TREA

3-heterocyclyl-substituted benzoyl derivatives

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Information

  • Patent Grant
  • 7608564
  • Patent Number
    7,608,564
  • Date Filed
    Wednesday, April 25, 2007
    17 years ago
  • Date Issued
    Tuesday, October 27, 2009
    15 years ago
Information
Abstract
Benzoyl derivatives of the formula I
Description

The present invention relates to 3-heterocyclyl-substituted benzoyl derivatives of the formula I




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where the variables have the following meanings:

  • R1, R2 are hydrogen, nitro, halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl or C1-C6-haloalkylsulfonyl;
  • R3 is hydrogen, halogen or C1-C6-alkyl;
  • R4, R5 are hydrogen, halogen, cyano, nitro, C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, di(C1-C4-alkoxy)-C1-C4-alkyl, di(C1-C4-alkyl)-amino-C1-C4-alkyl, [2,2-di(C1-C4-alkyl)-1-hydrazino]-C1-C4-alkyl, C1-C6-alkyliminooxy-C1-C4-alkyl, C1-C4-alkoxycarbonyl -C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-cyanoalkyl, C3-C8-cycloalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C2-C4-alkoxy, C1-C4-haloalkoxy, hydroxyl, C1-C4-alkylcarbonyloxy, C1-C4-alkylthio, C1-C4-haloalkylthio, di(C1-C4-alkyl)amino, COR6, phenyl or benzyl, it being possible for the two last-mentioned substituents to be fully or partially halogenated and/or to have attached to them one to three of the following groups:
    • nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;


      or
  • R4 and R5 together form a C2-C6-alkanediyl chain which can be mono-to tetrasubstituted by C1-C4-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C1-C4-alkyl;


    or
  • R4 and R5 together with the corresponding carbon form a carbonyl or thiocarbonyl group;
  • R6 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C2-C4-alkoxy, C1-C4-haloalkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy or NR7R8;
  • R7 is hydrogen or C1-C4-alkyl;
  • R8 is C1-C4-alkyl;
  • x is O, S, NR9, CO or CR10OR11;
  • Y is O, S, NR12, CO or CR13R14;
  • R9, R12 are hydrogen or C1-C4-alkyl;
  • R10, R11, R13, R14 are hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxycarbonyl, C1-C4-haloalkoxycarbonyl or CONR7R8;


    or
  • R4 and R9 or R4 and R10 or R5 and R12 or R5 and R13 together form a C2-C6-alkanediyl chain which can be mono- to tetrasubstituted by C1-C4-alkyl and/or interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C1-C4-alkyl;
  • R15 is a pyrazole of the formula II which is linked in the 4-position




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where

  • R16 is C1-C6-alkyl;
  • Z is H or S2R17;
  • R17 is C1-C4-alkyl, C1-C4-haloalkyl, phenyl or phenyl which is partially or fully halogenated and/or has attached to it one to three of the following groups:
  • nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
  • R18 is hydrogen or C1-C6-alkyl;


    where X and Y are not simultaneously oxygen or sulfur;


    with the exception of 4-[2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]-l-ethyl-5-hydroxy-lH-pyrazole, 4-[2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1,3-dimethyl-5-hydroxy-lH-pyrazole, 4-[2-chloro-3-(5-cyano-4,5-dihydroisoxazol-3-yl)-4-methyl-sulfonylbenzoyl]-1,3-dimethyl-5-hydroxy-lH-pyrazole, 4-[2-chloro-3-(4,5-dihydrothiazol-2-yl)-4-methylsulfonylbenzoyl]-1,3-dimethyl-5-hydroxy-lH-pyrazole and 4-[2-chloro-3- (thiazoline-4,5-dion-2-yl)-4-methylsulfonyl- benzoyl]-1,3-dimethyl-5-hydroxy-lH- pyrazole;


    or the agriculturally useful salts thereof.


The invention furthermore relates to processes and intermediates for the preparation of compounds of the formula I, to compositions comprising them, and to the use of these derivatives or compositions comprising them for the control of harmful plants.


Pyrazol-4-yl-benzoyl derivatives have been disclosed in the literature, for example in WO 96/26206.


However, the herbicidal properties of the compounds which have been known to date and their compatibility properties regarding crop plants are only moderately satisfactory.


It is an object of the present invention to provide novel, in particular herbicidally active, compounds which have improved properties.


We have found that this object is achieved by the 3-hetero-cyclyl-substituted benzoyl derivatives of the formula I and by their herbicidal activity.


We have furthermore found herbicidal compositions which comprise the compounds I and which have a very good herbicidal activity. Moreover, we have found processes for the preparation of these compositions and methods of controlling undesirable vegetation using the compounds I.


Depending on the substitution pattern, the compounds of the formula I can contain one or more chiral centers, in which case they exist as enantiomer or diastereomer mixtures. The present invention relates to the pure enantiomers or diastereomers and to the mixtures thereof.


The compounds of the formula I may also exist in the form of their agriculturally useful salts, the type of salt generally being of no importance. In general, suitable salts are the salts of those cations or the acid addition salts of those acids whose cations, or anions, respectively, do not adversely affect the herbicidal activity of the compounds I.


Suitable cations are, in particular, ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium and magnesium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium, it being possible in this case, if desired, for one to four hydrogen atoms to be replaced by C1-C4-alkyl, hydroxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, hydroxy-C1-C4-alkoxy-C1-C4-alkyl, phenyl or benzyl, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2-(2-hydroxyeth-1-oxy)eth-1-ylammonium, di(2-hydroxyeth-1-yl)ammonium, trimethylbenzylammonium, in addition phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium.


Anions of useful acid addition salts are mainly chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate.


The organic moieties mentioned for the substituents R1-R18 or as radicals on phenyl rings are collective terms for individual enumerations of the individual group members. All hydrocarbon chains, ie. all alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, alkyliminooxy, alkylcarbonyloxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkoxycarbonyl, haloalkoxycarbonyl, alkenyloxy, alkynyloxy, dialkylamino, dialkylhydrazino, alkoxyalkyl, hydroxyalkoxyalkyl, dialkoxyalkyl, alkylthioalkyl, dialkylaminoalkyl, dialkylhydrazinoalkyl, alkyliminooxyalkyl, alkoxycarbonylalkyl and alkoxyalkoxy moieties, can be straight-chain or branched. Unless otherwise specified, halogenated substituents preferably have attached to them one to five identical or different halogen atoms. The meaning of halogen is in each case fluorine, chlorine, bromine or iodine.


Other examples of meanings are:


C1-C4-alkyl and the alkyl moieties of di-(C1-C4-alkoxy)-C1-C4-alkyl, [2,2-di(C1-C4-alkyl)-1-hydrazino]-C1-C4-alkyl, C1-C6-alkyliminooxy-C1-C4-alkyl, hydroxy-C1-C4-alkoxy-C1-C4-alkyl and C1-C4-alkylcarbonyloxy: for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;


C1-C6-alkyl: C1-C4-alkyl as mentioned above and, for example, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-3-methylpropyl;


C1-C4-haloalkyl: a C1-C4-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl and nonafluorobutyl;


C1-C6-haloalkyl: C1-C4-haloalkyl as mentioned above and, for example, 5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl and dodecafluorohexyl;


C1-C4-cyanoalkyl: for example cyanomethyl, 1-cyanoeth-1-yl, 2-cyanoeth-1-yl, 1-cyanoprop-1-yl, 2-cyanoprop-1-yl, 3-cyanoprop-1-yl, 1-cyanoprop-2-yl, 2-cyanoprop-2-yl, 1-cyanobut-1-yl, 2-cyanobut-1-yl, 3-cyanobut-1-yl, 4-cyanobut-1-yl, 1-cyanobut-2-yl, 2-cyanobut-2-yl, 1-cyanobut-3-yl, 2-cyanobut-3-yl, 1-cyano-2-methylprop-3-yl, 2-cyano-2-methylprop-3-yl, 3-cyano-2-methylprop-3-yl and 2-cyanomethylprop-2-yl;


C1-C4-alkoxy and the alkoxy moieties of di-(C1-C4-alkoxy)-C1-C4-alkyl and hydroxy-C1-C4-alkoxy-C1-C4-alkyl: for example methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy;


C1-C6-alkoxy: C1-C4-alkoxy as mentioned above and, for example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methoxylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy and 1-ethyl-2-methylpropoxy;


C1-C4-haloalkoxy: a C1-C4-alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromomethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2,3-dichloropropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy, 1-(fluoromethyl)-2-fluoroethoxy, 1-(chloromethyl)-2-chloroethoxy, 1-(bromomethyl)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy and nonafluorobutoxy;


C1-C6-haloalkoxy: C1-C4-haloalkoxy as mentioned above and, for example, 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy and dodecafluorohexoxy;


C1-C6-alkyliminooxy and the C1-C6-akyliminooxy moieties of C1-C6-alkyliminooxy-C1-C4-alkyl: for example methyliminooxy, ethyliminooxy, 1-propyliminooxy, 2-propyliminooxy, 1-butyliminooxy, 2-butyliminooxy, 2-methylprop-1-yliminooxy, 1-pentyliminooxy, 2-pentyliminooxy, 3-pentyliminooxy, 3-methylbut-2-yliminoxy, 2-methylbut-1-yliminooxy, 3-methylbut-1-yliminooxy, 1-hexyliminooxy, 2-Hexyliminooxy, 3-hexyliminooxy, 2-methylpent-1-yliminooxy, 3-methylpent-1-yliminooxy, 4-methylpent-1-yliminooxy, 2-ethylbut-1-yliminooxy, 3-ethylbut-1-yliminooxy, 2,3-dimethylbut-1-yliminooxy, 3-methylpent-2-yliminooxy, 4-methylpent-2-yliminooxy and 3,3-dimethylbut-2-yliminooxy;


C1-C4-alkylthio: for example methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio and 1,1-dimethylethylthio;


C1-C6-alkylthio: C1-C4-alkylthio as mentioned above and, for example, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-1-methylpropylthio and 1-ethyl-2-methylpropylthio;


C1-C4-haloalkylthio: a C1-C4-alkylthio radical as mentioned above, which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, bromodifluoromethylthio, 2-fluorethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2,2,2-trichloroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, pentafluoroethylthio, 2-fluoropropylthio, 3-fluoropropylthio, 2-chloropropylthio, 3-chloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 2,2-difluoropropylthio, 2,3-difluoropropylthio, 2,3-dichloropropylthio, 3,3,3-trifluoropropylthio, 3,3,3-trichloropropylthio, 2,2,3,3,3-pentafluoropropylthio, heptafluoropropylthio, 1-(fluoromethyl)-2-fluoroethylthio, 1-(chloromethyl)-2-chloroethylthio, 1-(bromomethyl)-2-bromoethylthio, 4-fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio and nonafluorobutylthio;


C1-C6-haloalkylthio: C1-C4-haloalkylthio as mentioned above and, for example, 5-fluoropentylthio, 5-chloropentylthio, 5-bromopentylthio, 5-iodopentylthio, undecafluoropentylthio, 6-fluorohexylthio, 6-chlorohexylthio, 6-bromohexylthio, 6-iodohexylthio and dodecafluorohexylthio;


C1-C6-alkylsulfinyl(C1-C6-alkyl-S(═O)—): for example methylsulfinyl, ethylsulfinyl, propylsulfinyl, 1-methylethylsulfinyl, butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl, 1,1-dimethylethylsulfinyl, pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 2,2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, 1,1-dimethylpropylsulfinyl, 1,2-dimethylpropylsulfinyl, hexylsulfinyl, 1-methylpentylsulfinyl, 2-methylpentylsulfinyl, 3-methylpentylsulfinyl, 4-methylpentylsulfinyl, 1,1-dimethylbutylsulfinyl, 1,2-dimethylbutylsulfinyl, 1,3-dimethylbutylsulfinyl, 2,2-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl, 3,3-dimethylbutylsulfinyl, 1-ethylbutylsulfinyl, 2-ethylbutylsulfinyl, 1,1,2-trimethylpropylsulfinyl, 1,2,2-trimethylpropylsulfinyl, 1-ethyl-1-methylpropylsulfinyl and 1-ethyl-2-methylpropylsulfinyl;


C1-C6-haloalkylsulfinyl: a C1-C6-alkylsulfinyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example fluoromethylsulfinyl, difluoromethylsulfinyl, trifluoromethylsulfinyl, chlorodifluoromethylsulfinyl, bromodifluoromethylsulfinyl, 2-fluoroethylsulfinyl, 2-chloroethylsulfinyl, 2-bromoethylsulfinyl, 2-iodoethylsulfinyl, 2,2-difluoroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl, 2,2,2-trichloroethylsulfinyl, 2-chloro-2-fluoroethylsulfinyl, 2-chloro-2,2-difluoroethylsulfinyl, 2,2-dichloro-2-fluoroethylsulfinyl, pentafluoroethylsulfinyl, 2-fluoropropylsulfinyl, 3-fluoropropylsulfinyl, 2-chloropropylsulfinyl, 3-chloropropylsulfinyl, 2-bromopropylsulfinyl, 3-bromopropylsulfinyl, 2,2-difluoropropylsulfinyl, 2,3-difluoropropylsulfinyl, 2,3-dichloropropylsulfinyl, 3,3,3-trifluoropropylsulfinyl, 3,3,3-trichloropropylsulfinyl, 2,2,3,3,3-pentafluoropropylsulfinyl, heptafluoropropylsulfinyl, 1-(fluoromethyl)-2-fluoroethylsulfinyl, 1-(chloromethyl)-2-chloroethylsulfinyl, 1-(bromomethyl)-2-bromoethylsulfinyl, 4-fluorobutylsulfinyl, 4-chlorobutylsulfinyl, 4-bromobutylsulfinyl, nonafluorobutylsulfinyl, 5-fluoropentylsulfinyl, 5-chloropentylsulfinyl, 5-bromopentylsulfinyl, 5-iodopentylsulfinyl, undecafluoropentylsulfinyl, 6-fluorohexylsulfinyl, 6-chlorohexylsulfinyl, 6-bromohexylsulfinyl, 6-iodohexylsulfinyl and dodecafluorohexylsulfinyl;


C1-C6-alkylsulfonyl(C1-C6-alkyl-S(═O)2—): for example methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl, 1,1-dimethylethylsulfonyl, pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 1,1-dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl, 2,2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, hexylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1,1-dimethylbutylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl, 3,3-dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1,1,2-trimethylpropylsulfonyl, 1,2,2-trimethylpropylsulfonyl, 1-ethyl-1-methylpropylsulfonyl and 1-ethyl-2-methylpropylsulfonyl;


C1-C6-haloalkylsulfonyl: a C1-C6-alkylsulfonyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2-chloro-2,2-difluoroethylsulfonyl, 2,2-dichloro-2-fluoroethylsulfonyl, 2,2,2-trichloroethylsulfonyl, pentafluoroethylsulfonyl, 2-fluoropropylsulfonyl, 3-fluoropropylsulfonyl, 2-chloropropylsulfonyl, 3-chloropropylsulfonyl, 2-bromopropylsulfonyl, 3-bromopropylsulfonyl, 2,2-difluoropropylsulfonyl, 2,3-difluoropropylsulfonyl, 2,3-dichloropropylsulfonyl, 3,3,3-trifluoropropylsulfonyl, 3,3,3-trichloropropylsulfonyl, 2,2,3,3,3-pentafluoropropylsulfonyl, heptafluoropropylsulfonyl, 1-(fluoromethyl)-2-fluoroethylsulfonyl, 1-(chloromethyl)-2-chloroethylsulfonyl, 1-(bromomethyl)-2-bromoethylsulfonyl, 4-fluorobutylsulfonyl, 4-chlorobutylsulfonyl, 4-bromobutylsulfonyl, nonafluorobutylsulfonyl, 5-fluoropentylsulfonyl, 5-chloropentylsulfonyl, 5-bromopentylsulfonyl, 5-iodopentylsulfonyl, 6-fluorohexylsulfonyl, 6-bromohexylsulfonyl, 6-iodohexylsulfonyl and dodecafluorohexylsulfonyl;


C1-C4-alkoxycarbonyl: for example methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, 1-methylethoxycarbonyl, butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl and 1,1-dimethoxycarbonyl;


C1-C4-haloalkoxycarbonyl: a C1-C4-alkoxycarbonyl as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example fluoromethoxycarbonyl, difluoromethoxycarbonyl, trifluoromethoxycarbonyl, chlorodifluoromethoxycarbonyl, bromodifluoromethoxycarbonyl, 2-fluoroethoxycarbonyl, 2-chloroethoxycarbonyl, 2-bromoethoxycarbonyl, 2-iodoethoxycarbonyl, 2,2-difluoroethoxycarbonyl, 2,2,2-trifluoroethoxycarbonyl, 2-chloro-2-fluoroethoxycarbonyl, 2-chloro-2,2-difluoroethoxycarbonyl, 2,2-dichloro-2-fluoroethoxycarbonyl, 2,2,2-trichloroethoxycarbonyl, pentafluoroethoxycarbonyl, 2-fluoropropoxycarbonyl, 3-fluoropropoxycarbonyl, 2-chloropropoxycarbonyl, 3-chloropropoxycarbonyl, 2-bromopropoxycarbonyl, 3-bromopropoxycarbonyl, 2,2-difluoropropoxycarbonyl, 2,3-difluoropropoxycarbonyl, 2,3-dichloropropoxycarbonyl, 3,3,3-trifluoropropoxycarbonyl, 3,3,3-trichloropropoxycarbonyl, 2,2,3,3,3-pentafluoropropoxycarbonyl, heptafluoropropoxycarbonyl, 1-(fluoromethyl)-2-fluoroethoxycarbonyl, 1-(chloromethyl)-2-chloroethoxycarbonyl, 1-(bromomethyl)-2-bromoethoxycarbonyl, 4-fluorobutoxycarbonyl, 4-chlorobutoxycarbonyl, 4-bromobutoxycarbonyl and 4-iodobutoxycarbonyl;


C3-C6-alkenyloxy: for example prop-1-en-1-yloxy, prop-2-en-1-yloxy, 1-methylethenyloxy, buten-1-yloxy, buten-2-yloxy, buten-3-yloxy, 1-methylprop-1-en-1-yloxy, 2-methylprop-1-en-1-yloxy, 1-methylprop-2-en-1-yloxy, 2-methylprop-2-en-1-yloxy, penten-1-yloxy, penten-2-yloxy, penten-3-yloxy, penten-4-yloxy, 1-methylbut-1-en-1-yloxy, 2-methylbut-1-en-1-yloxy, 3-methylbut-1-en-1-yloxy, 1-methylbut-2-en-1-yloxy, 2-methylbut-2-en-1-yloxy, 3-methylbut-2-en-1-yloxy, 1-methylbut-3-en-1-yloxy, 2-methylbut-3-en-1-yloxy, 3-methylbut-3-en-1-yloxy, 1,1-dimethylprop-2-en-1-yloxy, 1,2-dimethylprop-1-en-1-yloxy, 1,2-dimethylprop-2-en-1-yloxy, 1-ethylprop-1-en-2-yloxy, 1-ethylprop-2-en-1-yloxy, hex-1-en-1-yloxy, hex-2-en-1-yloxy, hex-3-en-1-yloxy, hex-4-en-1-yloxy, hex-5-en-1-yloxy, 1-methylpent-1-en-1-yloxy, 2-methylpent-1-en-1-yloxy, 3-methylpent-1-en-1-yloxy, 4-methylpent-1-en-1-yloxy, 1-methylpent-2-en-1-yloxy, 2-methylpent-2-en-1-yloxy, 3-methylpent-2-en-1-yloxy, 4-methylpent-2-en-1-yloxy, 1-methylpent-3-en-1-yloxy, 2-methylpent-3-en-1-yloxy, 3-methylpent-3-en-1-yloxy, 4-methylpent-3-en-1-yloxy, 1-methylpent-4-en-1-yloxy, 2-methylpent-4-en-1-yloxy, 3-methylpent-4-en-1-yloxy, 4-methylpent-4-en-1-yloxy, 1,1-dimethylbut-2-en-1-yloxy, 1,1-dimethylbut-3-en-1-yloxy, 1,2-dimethylbut-1-en-1-yloxy, 1,2-dimethylbut-2-en-1-yloxy, 1,2-dimethylbut-3-en-1-yloxy, 1,3-dimethylbut-1-en-1-yloxy, 1,3-dimethylbut-2-en-1-yloxy, 1,3-dimethylbut-3-en-1-yloxy, 2,2-dimethylbut-3-en-1-yloxy, 2,3-dimethylbut-1-en-1-yloxy, 2,3-dimethylbut-2-en-1-yloxy, 2,3-dimethylbut-3-en-1-yloxy, 3,3-dimethylbut-1-en-1-yloxy, 3,3-dimethylbut-2-en-1-yloxy, 1-ethylbut-1-en-1-yloxy, 1-ethylbut-2-en-1-yloxy, 1-ethylbut-3-en-1-yloxy, 2-ethylbut-1-en-1-yloxy, 2-ethylbut-2-en-1-yloxy, 2-ethylbut-3-en-1-yloxy, 1,1,2-trimethylprop-2-en-1-yloxy, 1-ethyl-1-methylprop-2-en-1-yloxy, 1-ethyl-2-methylprop-1-en-1-yloxy and 1-ethyl-2-methylprop-2-en-1-yloxy;


C3-C6-alkynyloxy: for example prop-1-yn-1-yloxy, prop-2-yn-1-yloxy, but-1-yn-1-yloxy, but-1-yn-3-yloxy, but-1-yn-4-yloxy, but-2-yn-1-yloxy, pent-1-yn-1-yloxy, pent-1-yn-3-yloxy, pent-1-yn-4-yloxy, pent-1-yn-5-yloxy, pent-2-yn-1-yloxy, pent-2-yn-4-yloxy, pent-2-yn-5-yloxy, 3-methylbut-1-yn-3-yloxy, 3-methylbut-1-yn-4-yloxy, hex-1-yn-1-yloxy, hex-1-yn-3-yloxy, hex-1-yn-4-yloxy, hex-1-yn-5-yloxy, hex-1-yn-6-yloxy, hex-2-yn-1-yloxy, hex-2-yn-4-yloxy, hex-2-yn-5-yloxy, hex-2-yn-6-yloxy, hex-3-yn-1-yloxy, hex-3-yn-2-yloxy, 3-methylpent-1-yn-1-yloxy, 3-methylpent-1-yn-3-yloxy, 3-methylpent-1-yn-4-yloxy, 3-methylpent-1-yn-5-yloxy, 4-methylpent-1-yn-1-yloxy, 4-methylpent-2-yn-4-yloxy and 4-methylpent-2-yn-5-yloxy;


di(C1-C4-alkyl)amino: for example N,N-dimethylamino, N,N-diethylamino, N,N-dipropylamino, N,N-di(1-methylethyl)amino, N,N-dibutylamino, N,N-di(1-methylpropyl)amino, N,N-di(2-methylpropyl)amino, N,N-di(1,1-dimethylethyl)amino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-methyl-N-(1-methylethyl)amino, N-butyl-N-methylamino, N-methyl-N-(1-methylpropyl)amino, N-methyl-N-(2-methylpropyl)amino, N-(1,1-dimethylethyl)-N-methylamino, N-ethyl-N-propylamino, N-ethyl-N-(1-methylethyl)amino N-butyl-N-ethylamino, N-ethyl-N-(1-methylpropyl)amino, N-ethyl-N-(2-methylpropyl)amino, N-ethyl-N-(1,1-dimethylethyl)amino, N-(1-methylethyl)-N-propylamino, N-butyl-N-propylamino, N-(1-methylpropyl)-N-propylamino, N-(2-methylpropyl) -N-propylamino, N-(1,1-dimethylethyl)-N-propylamino, N-butyl-N-(1-methylethyl)amino, N-(1-methylethyl)-N-(1-methylpropyl)amino, N-(1-methylethyl)-N-(2-methylpropyl)amino, N-(1,1-dimethylethyl)-N-(1-methylethyl)amino, N-butyl-N-(1-methylpropyl)amino, N-butyl-N-(2-methylpropyl)amino, N-butyl-N-(1,1-dimethylethyl)amino, N-(1-methylpropyl)-N-(2-methylpropyl)amino, N-(1,1-dimethylethyl)-N-(1-methylpropyl)amino and N-(1,1-dimethylethyl)-N-(2-methylpropyl)amino;


[2,2-di(C1-C4-alkyl)-1-hydrazino], and the dialkylhydrazino moieties of [2,2-di(C1-C4-alkyl)-1-hydrazino]-C1-C4-alkyl: for example 2,2-dimethylhydrazino-1,2,2-diethylhydrazino-1,2,2-dipropylhydrazino-1,2,2-di(1-methylethyl)-1-hydrazino, 2,2-dibutylhydrazino-1,2,2-di(1-methylpropyl)-1-hydrazino, 2,2-di(2-methylpropyl)-1-hydrazino, 2,2-di(1,1-dimethylethyl)-1-hydrazino, 2-ethyl-2-methyl-1-hydrazino, 2-methyl-2-propyl-1-hydrazino, 2-methyl-2-(1-methylethyl)-1-hydrazino, 2-butyl-2-methyl-1-hydrazino, 2-methyl-2-(1-methylpropyl)-1-hydrazino, 2-methyl-2-(2-methylpropyl)-1-hydrazino, 2-(1,1-dimethylethyl)-2-methyl-1-hydrazino, 2-ethyl-2-propyl-1-hydrazino, 2-ethyl-2-(1-methylethyl)-1-hydrazino, 2-butyl-2-ethyl-1-hydrazino, 2-ethyl-2-(1-methylpropyl)-1-hydrazino, 2-ethyl-2-(2-methylpropyl)-1-hydrazino, 2-ethyl-2-(1,1-dimethylethyl)-1-hydrazino, 2-(1-methylethyl)-2-propyl-1-hydrazino, 2-butyl-2-propyl-1-hydrazino, 2-(1-methylpropyl)-2-propyl-1-hydrazino, 2-(2-methylpropyl)-2-propyl-1-hydrazino, 2-(1,1-dimethylethyl)-2-propyl-1-hydrazino, 2-butyl-2-(1-methylethyl)-1-hydrazino, 2-(1-methylethyl)-2-(1-methylpropyl)-1-hydrazino, 2-(1-methylethyl)-2-(2-methylpropyl)-1-hydrazino, 2-(1,1-dimethylethyl)-2-(1-methylethyl)-1-hydrazino, 2-butyl-2-(1-methylpropyl)-1-hydrazino, 2-butyl-2-(2-methylpropyl)-1-hydrazino, 2-butyl-2-(1,1-dimethylethyl)-1-hydrazino, 2-(1-methylpropyl)-2-(2-methylpropyl)-1-hydrazino, 2-(1,1-dimethylethyl)-2-(1-methylpropyl)-1-hydrazino and 2-(1,1-dimethylethyl)-2-(2-methylpropyl)-1-hydrazino;


di(C1-C4-alkyl)amino-C1-C4-alkyl: C1-C4-alkyl which is substituted by di(C1-C4-alkyl)amino as mentioned above, for example N,N-dimethylaminomethyl, N,N-diethylaminomethyl, N,N-dipropylaminomethyl, N,N-di(1-methylethyl)aminomethyl, N,N-dibutylaminomethyl, N,N-di(1-methylpropyl)aminomethyl, N,N-di(2-methylpropyl)aminomethyl, N,N-di(1,1-dimethylethyl)aminomethyl, N-ethyl-N-methylaminomethyl, N-methyl-N-propylaminomethyl, N-methyl-N-(1-methylethyl)aminomethyl, N-butyl-N-methylaminomethyl, N-methyl-N-(1-methylpropyl)aminomethyl, N-methyl-N-(2-methylpropyl)aminomethyl, N-(1,1-dimethylethyl)-N-methylaminomethyl, N-ethyl-N-propylaminomethyl, N-ethyl-N-(1-methylethyl)aminomethyl, N-butyl-N-ethylaminomethyl, N-ethyl-N-(1-methylpropyl)aminomethyl, N-ethyl-N-(2-methylpropyl)aminomethyl, N-ethyl-N-(1,1-di-methylethyl)aminomethyl, N-(1-methylethyl)-N-propylaminomethyl, N-butyl-N-propylaminomethyl, N-(1-methylpropyl)-N-propylaminomethyl, N-(2-methylpropyl)-N-propylaminomethyl, N-(1,1-dimethylethyl)-N-propylaminomethyl, N-butyl-N-(1-methylethyl)aminomethyl, N-(1-methylethyl)-N-(1-methylpropyl)aminomethyl, N-(1-methylethyl)-N-(2-methylpropyl)aminomethyl, N-(1,1-dimethylethyl)-N-(1-methylethyl)aminomethyl, N-butyl-N-(1-methylpropyl)aminomethyl, N-butyl-N-(2-methylpropyl)aminomethyl, N-butyl-N-(1,1-dimethylethyl)aminomethyl, N-(1-methylpropyl)-N-(2-methylpropyl)aminomethyl, N-(1,1-dimethylethyl)-N-(1-methylpropyl)aminomethyl, N-(1,1-dimethylethyl)-N-(2-methylpropyl)aminomethyl, 2-(N,N-dimethylamino)ethyl, 2-(N,N-diethylamino)ethyl, 2-(N,N-dipropylamino)ethyl, 2-[N,N-di(1-methylethyl)amino]ethyl, 2-[N,N-dibutylamino]ethyl, 2-[N,N-di(1-methylpropyl)amino]ethyl, 2-[N,N-di(2-methylpropyl)amino]ethyl, 2-[N,N-di(1,1-dimethylethyl)amino]ethyl, 2-[N-ethyl-N-methylamino]ethyl, 2-[N-methyl-N-propylamino]ethyl, 2-[N-methyl-N-(1-methylethyl)amino]ethyl, 2-[N-butyl-N-methylamino]ethyl, 2-[N-methyl-N-(1-methylpropyl)amino]ethyl, 2-[N-methyl-N-(2-methylpropyl)amino]ethyl, 2-[N-(1,1-dimethylethyl)-N-methylamino]ethyl, 2-[N-ethyl-N-propylamino]ethyl, 2-[N-ethyl-N-(1-methylethyl)amino]ethyl, 2-[N-butyl-N-ethylamino]ethyl, 2-[N-ethyl-N-(1-methylpropyl)amino]ethyl, 2-[N-ethyl-N-(2-methylpropyl)amino]ethyl, 2-[N-ethyl-N-(1,1-dimethylethylamino]ethyl, 2-[N-(1-methylethyl)-N-propylamino]ethyl, 2-[N-butyl-N-propylamino]ethyl, 2-[N-(1-methylpropyl)-N-propylamino]ethyl, 2-[N-(2-methylpropyl)-N-propylamino]ethyl, 2-[N-(1,1-dimethylethyl)-N-propylamino]ethyl, 2-[N-butyl-N-(1-methylethyl)amino]ethyl, 2-[N-(1-methylethyl)-N-(1-methylpropyl)amino]ethyl, 2-[N-(1-methylethyl)-N-(2-methylpropyl)amino]ethyl, 2-[N-(1,1-dimethylethyl)-N-(1-methylethyl)amino]ethyl, 2-[N-butyl-N-(1-methylpropyl)amino]ethyl, 2-[N-butyl-N-(2-methylpropyl)amino]ethyl,2-[N-butyl-N-(1,1-dimethylethyl)amino]ethyl, 2-[N-(1-methylpropyl)-N-(2-methylpropyl)amino]ethyl, 2-[N-(1,1-dimethylethyl)-N-(1-methylpropyl)amino]ethyl, 2-[N-(1,1-dimethylethyl)-N-(2-methylpropyl)amino]ethyl, 3-(N,N-dimethylamino)propyl, 3-(N,N-diethylamino)propyl, 4-(N,N-dimethylamino)butyl and 4-(N,N-diethylamino)butyl;


C1-C4-alkoxy-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-alkoxy as mentioned above, for example methoxymethyl, ethoxymethyl, propoxymethyl, (1-methylethoxy)methyl, butoxymethyl, (1-methylpropoxy)methyl, (2-methylpropoxy)methyl, (1,1-dimethylethoxy)methyl, 2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2-(propoxy)ethyl, 2-(1-methylethoxy)ethyl, 2-(butoxy)ethyl, 2-(1-methylpropoxy)ethyl, 2-(2-methylpropoxy)ethyl, 2-(1,1-dimethylethoxy)ethyl, 2-(methoxy)-propyl, 2-(ethoxy)propyl, 2-(propoxy)propyl, 2-(1-methylethoxy)propyl, 2-(butoxy)propyl, 2-(1-methylpropoxy)propyl, 2-(2-methylpropoxy)propyl, 2-(1,1-dimethylethoxy)propyl, 3-(methoxy)propyl, 3-(ethoxy)-propyl, 3-(propoxy)propyl, 3-(1-methylethoxy)propyl, 3-(butoxy)propyl, 3-(1-methylpropoxy)propyl, 3-(2-methylpropoxy)propyl, 3-(1,1-dimethylethoxy)propyl, 2-(methoxy)butyl, 2-(ethoxy)butyl, 2-(propoxy)butyl, 2-(1-methylethoxy)butyl, 2-(butoxy)butyl, 2-(1-methylpropoxy)butyl, 2-(2-methylpropoxy)butyl, 2-(1,1-dimethylethoxy)butyl, 3-(methoxy)butyl, 3-(ethoxy)butyl, 3-(propoxy)butyl, 3-(1-methylethoxy)butyl, 3-(butoxy)butyl, 3-(1-methylpropoxy)butyl, 3-(2-methylpropoxy)butyl, 3-(1,1-dimethylethoxy)butyl, 4-(methoxy)butyl, 4-(ethoxy)butyl, 4-(propoxy)butyl, 4-(1-methylethoxy)butyl, 4-(butoxy)butyl, 4-(1-methylpropoxy)butyl, 4-(2-methylpropoxy)butyl and 4-(1,1-dimethylethoxy)butyl;


C1-C4-alkylthio-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-alkylthio as mentioned above, for example methylthiomethyl, ethylthiomethyl, propylthiomethyl, (1-methylethylthio)methyl, butylthiomethyl, (1-methylpropylthio)methyl, (2-methylpropylthio)methyl, (1,1-dimethylethylthio)methyl, 2-methylthioethyl, 2-ethylthioethyl, 2-(propylthio)ethyl, 2-(1-methylethylthio)ethyl, 2-(butylthio)ethyl, 2-(1-methylpropylthio)ethyl, 2-(2-methylpropylthio)ethyl, 2-(1,1-dimethylethylthio)ethyl, 2-(methylthio)propyl, 3-(methylthio)propyl, 2-(ethylthio)propyl, 3-(ethylthio)propyl, 3-(propylthio)propyl, 3-(butylthio)propyl, 4-(methylthio)butyl, 4-(ethylthio)butyl, 4-(propylthio)butyl and 4-(butylthio)butyl;


C1-C4-alkoxycarbonyl-C1-C4-alkyl: C1-C4-alkyl which is substituted by C1-C4-alkoxycarbonyl as mentioned above, for example methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, (1-methylethoxycarbonyl)methyl, butoxycarbonylmethyl, (1-methylpropoxycarbonyl)methyl, (2-methylpropoxycarbonyl)methyl, (1,1-dimethylethoxycarbonyl)methyl, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(propoxycarbonyl)ethyl, 2-(1-methylethoxycarbonyl)ethyl, 2-(butoxycarbonyl)ethyl, 2-(1-methylpropoxycarbonyl)ethyl, 2-(2-methylpropoxycarbonyl)ethyl, 2-(1,1-dimethylethoxycarbonyl)ethyl, 2-(methoxycarbonyl)propyl, 2-(ethoxycarbonyl)propyl, 2-(propoxycarbonyl)propyl, 2-(1-methylethoxycarbonyl)propyl, 2-(butoxycarbonyl)propyl, 2-(1-methylpropoxycarbonyl)propyl, 2-(2-methylpropoxycarbonyl)propyl, 2-(1,1-dimethylethoxycarbonyl)propyl, 3-(methoxycarbonyl)propyl, 3-(ethoxycarbonyl)propyl, 3-(propoxycarbonyl)propyl, 3-(1-methylethoxycarbonyl)propyl, 3-(butoxycarbonyl)propyl, 3-(1-methylpropoxycarbonyl)propyl, 3-(2-methylpropoxycarbonyl)propyl, 3-(1,1-dimethylethoxycarbonyl)propyl, 2-(methoxycarbonyl)butyl, 2-(ethoxycarbonyl)butyl, 2-(propoxycarbonyl)butyl, 2-(1-methylethoxycarbonyl)butyl, 2-(butoxycarbonyl)butyl, 2-(1-methylpropoxycarbonyl)butyl, 2-(2-methylpropoxycarbonyl)butyl, 2-(1,1-dimethylethoxycarbonyl)butyl, 3-(methoxycarbonyl)butyl, 3-(ethoxycarbonyl)butyl, 3-(propoxycarbonyl)butyl, 3-(1-methylethoxycarbonyl)butyl, 3-(butoxycarbonyl)butyl, 3-(1-methylpropoxycarbonyl)butyl, 3-(2-methylpropoxycarbonyl)butyl, 3-(1,1-dimethylethoxycarbonyl)butyl, 4-(methoxycarbonyl)-butyl, 4-(ethoxycarbonyl)butyl, 4-(propoxycarbonyl)butyl, 4-(1-methylethoxycarbonyl)butyl, 4-(butoxycarbonyl)butyl, 4-(1-methylpropoxy)butoxy, 4-(2-methylpropoxy)butoxy und 4-(1,1-dimethylethoxycarbonyl)butyl;


C1-C4-alkoxy-C2-C4-alkoxy: C2-C4-alkoxy which is substituted by C1-C4-alkoxy as mentioned above, for example 2-(methoxy)ethoxy, 2-(ethoxy)ethoxy, 2-(propoxy)ethoxy, 2-(1-methylethoxy)ethoxy, 2-(butoxy)ethoxy, 2-(1-methylpropoxy)ethoxy, 2-(2-methylpropoxy)ethoxy, 2-(1,1-dimethylethoxy)ethoxy, 2-(methoxy)propoxy, 2-(ethoxy)propoxy, 2-(propoxy)propoxy, 2-(1-methylethoxy)propoxy, 2-(butoxy)propoxy, 2-(1-methylpropoxy)propoxy, 2-(2-methylpropoxy)propoxy, 2-(1,1-dimethylethoxy)propoxy, 3-(methoxy)propoxy, 3-(ethoxy)propoxy, 3-(propoxy)propoxy, 3-(1-methylethoxy)propoxy, 3-(butoxy)propoxy, 3-(1-methylpropoxy)propoxy, 3-(2-methylpropoxy)propoxy, 3-(1,1-dimethylethoxy)propoxy, 2-(methoxy)butoxy, 2-(ethoxy)butoxy, 2-(propoxy)butoxy, 2-(1-methylethoxy)butoxy, 2-(butoxy)butoxy, 2-(1-methylpropoxy)butoxy, 2-(2-methylpropoxy)butoxy, 2-(1,1-dimethylethoxy)butoxy, 3-(methoxy)butoxy, 3-(ethoxy)-butoxy, 3-(propoxy)butoxy, 3-(1-methylethoxy)butoxy, 3-(butoxy)butoxy, 3-(1-methylpropoxy)butoxy, 3-(2-methylpropoxy)butoxy, 3-(1,1-dimethylethoxy)butoxy, 4-(methoxy)butoxy, 4-(ethoxy)butoxy, 4-(propoxy)butoxy, 4-(1-methylethoxy)butoxy, 4-(butoxy)butoxy, 4-(1-methylpropoxy)butoxy, 4-(2-methylpropoxy)butoxy and 4-(1,1-dimethylethoxy)butoxy;


C2-C6-alkanediyl: for example ethane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl and hexane-1,6-diyl;


C3-C8-cycloalkyl: for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl;


All phenyl rings are preferably unsubstituted or have attached to them one to three halogen atoms and/or a nitro group, a cyano radical and/or one or two methyl, trifluoromethyl, methoxy or trifluoromethoxy substituents.


Preference is given to the 3-heterocyclyl-substituted benzoyl derivatives of the formula I where the variables have the following meanings:

  • R1, R2 are hydrogen, nitro, halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl or C1-C6-haloalkylsulfonyl;
  • R3 is hydrogen, halogen or C1-C6-alkyl;
  • R4, R5 are hydrogen, halogen, cyano, nitro, C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, di(C1-C4-alkoxy)-C1-C4-alkyl, di(C1-C4-alkyl)-amino-C1-C4-alkyl, [2,2-di(C1-C4-alkyl)-1-hydrazino]-C1-C4-alkyl, C1-C6-alkyliminooxy-C1-C4-alkyl, C1-C4-alkoxycarbonyl-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-cyanoalkyl, C3-C8-cycloalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C2-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, di(C1-C4-alkyl)amino, COR6, phenyl or benzyl, it being possible for the two last-mentioned substituents to be fully or partially halogenated and/or to have attached to them one to three of the following groups:
    • nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;


      or
  • R4 and R5 together form a C2-C6-alkanediyl chain which can be mono-to tetrasubstituted by C1-C4-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted [lacuna] C1-C4-alkyl;


    or
  • R4 and R5 together with the corresponding carbon form a carbonyl or thiocarbonyl group;
  • R6 is C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C2-C4-alkoxy, C1-C4-haloalkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy or NR7R8;
  • R7 is hydrogen or C1-C4-alkyl;
  • R8 is C1-C4-alkyl;
  • X is O, S, NR9, CO or CR10R11;
  • Y is O, S, NR12, CO or CR13R14;
  • R9, R12 are hydrogen or C1-C4-alkyl;
  • R10, R11, R13, R14 are hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxycarbonyl, C1-C4-haloalkoxycarbonyl or CONR7R8;


    or
  • R4 and R9 or R4 and R10 or R5 and R12 or R5 and R13 together form a C2-C6-alkanediyl chain which can be mono- to tetrasubstituted by C1-C4-alkyl and/or interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C1-C4-alkyl;
  • R15 is a pyrazole of the formula II which is linked in the 4-position




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    • where



  • R16 is C1-C6-alkyl;

  • Z is H or SO2R17;

  • R17 is C1-C4-alkyl, C1-C4-haloalkyl, phenyl or phenyl which is partially or fully halogenated and/or has attached to it one to three of the following groups:

  • nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;

  • R18 is hydrogen or C1-C6-alkyl;


    where X and Y are not simultaneously oxygen or sulfur;



with the exception of 4-[2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]-1-ethyl-5-hydroxy-1H-pyrazole, 4-[2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1,3-dimethyl-5-hydroxy-1H-pyrazole, 4-[2-chloro-3-(5-cyano-4,5-dihydroisoxazol-3-yl)-4-methyl-sulfonylbenzoyl]-1,3-dimethyl-5-hydroxy-1H-pyrazole, 4-[2-chloro-3-(4,5-dihydrothiazol-2-yl)-4-methylsulfonylbenzoyl]-1,3-dimethyl-5-hydroxy-1H-pyrazole and 4-[2-chloro-3-(thiazoline-4,5-dion-2-yl)-4-methylsulfonyl-benzoyl]-1,3-dimethyl-5-hydroxy-1H-pyrazole;


or the agriculturally useful salts thereof.


With a view to the use of the compounds of the formula I according to the invention as herbicides, the variables preferably have the following meanings, in each case alone or in combination:

  • R1, R2 are nitro, halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl,C1-C6-alkylsulfonyl or C1-C6-haloalkylsulfonyl;
    • especially preferably nitro, halogen such as, for example, chlorine and bromine, C1-C6-alkyl such as, for example, methyl and ethyl, C1-C6-alkoxy such as, for example, methoxy and ethoxy, C1-C6-haloalkyl such as, for example, difluoromethyl and trifluoromethyl, C1-C6-alkylthio such as, for example, methylthio and ethylthio, C1-C6-alkylsulfinyl such as, for example, methylsulfinyl and ethylsulfinyl, C1-C6-alkylsulfonyl such as, for example, methylsulfonyl, ethylsulfonyl and propylsulfonyl or C1-C6-haloalkylsulfonyl such as, for example, trifluoromethylsulfonyl and pentafluoroethylsulfonyl;
  • R3 is hydrogen;
  • R4, R5 are hydrogen, halogen, cyano, nitro, C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, di(C1-C4-alkoxy)-C1-C4-alkyl, di(C1-C4-alkyl)amino-C1-C4-alkyl, [2,2-di(C1-C4-alkyl)hydrazino-1]-C1-C4-alkyl, C1-C6-alkyliminooxy-C1-C4-alkyl, C1-C4-alkoxycarbonyl-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-cyanoalkyl, C3-C8-cycloalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C2-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, di(C1-C4-alkyl)amino, COR6, phenyl or benzyl, it being possible for the two last-mentioned substituents to be partially or fully halogenated and/or to have attached to them one to three of the following groups:
    • nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;


      or
  • R4 and R5 together form a C2-C6-alkanediyl chain which can be mono-to tetrasubstituted by C1-C4-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C1-C4-alkyl;
    • R4 is especially preferably hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxycarbonyl or CONR7R8;
    • R5 is especially preferably hydrogen or C1-C4-alkyl; or
    • R4 and R5 especially preferably form a C2-C6-alkanediyl chain which can be mono- to tetrasubstituted by C1-C4-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C1-C4-alkyl;
  • R6 is C1-C4-alkyl, C1-C4-alkoxy or NR7R8;
  • R7 is hydrogen or C1-C4-alkyl;
  • R8 is C1-C4-alkyl;
  • X is O, S, NR9, CO or CR10R11;
  • Y is O, S, NR12 or CR13R14;
  • R9, R12 are hydrogen or C1-C4-alkyl;
  • R10, R11, R13, R14 are hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxycarbonyl, C1-C4-haloalkoxycarbonyl or CONR7R8;


    or
  • R4 and R9 or R4 and R10 or R5 and R12 or R5 and R13 together form a C2-C6-alkanediyl chain which can be mono-to tetrasubstituted by C1-C4-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C1-C4-alkyl;
  • R16 is C1-C6-alkyl;
    • especially preferably methyl, ethyl, propyl, 2-methylpropyl or butyl;
  • Z is H or SO2R17;
  • R17 is C1-C4-alkyl, phenyl or phenyl which is partially or fully halogenated and/or has attached to it one to three of the following groups:
    • nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
  • R18 is hydrogen or C1-C6-alkyl;
    • especially preferably hydrogen or methyl.


The following embodiments of the 3-heterocyclyl-substituted benzoyl derivatives of the formula I must be emphasized:

  • 1. In a preferred embodiment of the 3-heterocyclyl-substituted benzoyl derivatives of the formula I, Z is SO2R17.
    • Especially preferred are the 3-heterocyclyl-substituted benzoyl derivatives of the formula I, where R18 is hydrogen.
    • Also especially preferred are 3-heterocyclyl-substituted benzoyl derivatives of the formula I, where R18 is methyl.
      • Particularly preferred are 3-heterocylyl-substituted benzoyl derivatives of the formula I, where R17 is C1-C4-alkyl.
  • 2. In a further preferred embodiment of the 3-heterocyclyl-substituted benzoyl derivatives of the formula I, Z is hydrogen.
    • Especially preferred are 3-heterocyclyl-substituted benzoyl derivatives of the formula I where X is oxygen and Y is CR13R14.
      • Particularly preferred are 3-heterocyclyl-substituted benzoyl derivatives of the formula I where
        • R4 is halogen, nitro, C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxycarbonyl-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-cyanoalkyl, C3-C8-cycloalkyl, C1-C4-alkoxy, C1-C4-Alkoxy-C2-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, di(C1-C4-alkyl)amino, COR6, phenyl or benzyl, it being possible for the two last-mentioned substituents to be partially or fully halogenated and/or to have attached to them one to three of the following groups:
          • nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
        • R5 is hydrogen or C1-C4-alkyl;
        • or
        • R4 and R5 together form a C2-C6-alkanediyl chain which can be mono- to tetrasubstituted by C1-C4-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C1-C4-alkyl;
        • or
        • R5 and R13 together form a C2-C6-alkanediyl chain which can be mono- to tetrasubstituted by C1-C4-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C1-C4-alkyl.
        • Extraordinarily preferred are 3-heterocyclyl-substituted benzoyl derivatives of the formula I where
        • R4 is C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxycarbonyl or CONR7R8;
        • R5 is hydrogen or C1-C4-alkyl;
        • or
        • R4 and R5 together form a C2-C6-alkanediyl chain which can be mono- to tetrasubstituted by C1-C4-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C1-C4-alkyl;
        • or
        • R5 and R13 together form a C2-C6-alkanediyl chain which can be mono- to tetrasubstituted by C1-C4-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C1-C4-alkyl.
        • Especially extraordinarily preferred are 3-heterocyclyl-substituted benzoyl derivatives of the formula I where R18 is hydrogen.
      • Also particularly preferred are 3-heterocyclyl-substituted benzoyl derivatives of the formula I where R4 and R5 are hydrogen.
        • Extraordinarily preferred are 3-heterocyclyl-substituted benzoyl derivatives of the formula I where R18 is hydrogen.
          • Especially extraordinarily preferred are 3-heterocyclyl-substituted benzoyl derivatives of the formula I where
          • R1 is nitro, C1-C6-alkyl such as, for example, methyl and ethyl, C1-C6-alkoxy such as, for example, methoxy and ethoxy, C1-C6-haloalkyl such as, for example, difluoromethyl and trifluoromethyl, C1-C6-alkylsulfonyl such as, for example, methylsulfonyl, ethylsulfonyl and propylsulfonyl, or C1-C6-haloalkylsulfonyl such as, for example, trifluoromethylsulfonyl and pentafluoroethylsulfonyl;
          • Also especially extraordinarily preferred are 3-heterocyclyl-substituted benzoyl derivatives of the formula I where
          • R2 is nitro, halogen such as, for example, chlorine and bromine, C1-C6-alkyl such as, for example, methyl and ethyl, C1-C6-haloalkyl such as, for example, difluoromethyl and trifluoromethyl, C1-C6-alkylthio such as, for example, methylthio and ethylthio, C1-C6-alkylsulfinyl such as, for example, methylsulfinyl and ethylsulfinyl, C1-C6-alkylsulfonyl such as, for example, methylsulfonyl, ethylsulfonyl and propylsulfonyl, or C1-C6-haloalkylsulfonyl such as, for example, trifluomethylsulfonyl and pentafluoroethylsulfonyl.
        • Also especially extraordinarily preferred is 4-[2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]-1-methyl-5-hydroxy-1H-pyrazole.
          • Also especially extraordinarily preferred are the agriculturally useful salts of 4-[2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1-methyl-5-hydroxy-1H-pyrazole, in particular the alkali metal salts, such as, for example, lithium, sodium and potassium, and the ammonium salts, it being possible in this case, if desired, for one to four hydrogen atoms to be replaced by C1-C4-alkyl, hydroxy-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, hydroxy-C1-C4-alkoxy-C1-C4-alkyl, phenyl or benzyl, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2-(2-hydroxyeth-1-oxy)eth-1-ylammonium, di(2-hydroxyeth-1-yl)ammonium, trimethylbenzylammonium.
          • Also extraordinarily preferred are 3-heterocyclyl-substituted benzoyl derivatives of the formula I where R18 is methyl.
          • Especially extraordinarily preferred are 3-heterocyclyl-substituted benzoyl derivatives of the formula I where
          • R1 is nitro, C1-C6-alkyl such as, for example, methyl and ethyl, C1-C6-alkoxy such as, for example, methoxy and ethoxy, C1-C6-haloalkyl such as, for example, difluoromethyl and trifluoromethyl, C1-C6-alkylsulfonyl such as, for example, methylsulfonyl, ethylsulfonyl and propylsulfonyl, or C1-C6-haloalkylsulfonyl, for example trifluoromethylsulfonyl and pentafluoroethylsulfonyl.
          • Also especially extraordinarily preferred are 3-heterocyclyl-substituted benzoyl derivatives of the formula I where
          • R2 is nitro, halogen such as, for example, chlorine and bromine, C1-C6-alkyl such as, for example, methyl and ethyl, C1-C6-haloalkyl such as, for example, difluoromethyl and trifluoromethyl, C1-C6-alkylthio such as, for example, methylthio and ethylthio, C1-C6-alkylsulfinyl such as, for example, methylsulfinyl and ethylsulfinyl, C1-C6-alkylsulfonyl such as, for example, methylsulfonyl, ethylsulfonyl and propylsulfonyl, or C1-C6-haloalkylsulfonyl such as, for example, trifluoromethylsulfonyl and pentafluoroethylsulfonyl.
        • Also especially preferred are 3-heterocyclyl-substituted benzoyl derivatives of the formula I where
      • X is S, NR9, CO or CR10OR11;
      • or
      • Y is O, S, NR12 or CO.
      • Particularly preferred are 3-heterocyclyl-substituted benzoyl derivatives of the formula I where R18 is hydrogen.
      • Also particularly preferred are 3-heterocyclyl-substituted benzoyl derivatives of the formula I where R18 is C1-C6-alkyl.
        • Extraordinarily preferred are 3-heterocyclyl-substituted benzoyl derivatives of the formula I where
          • R4 is halogen, cyano, nitro, C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxycarbonyl-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-cyanoalkyl, C3-C8-cycloalkyl, C1-C6-alkoxy, C1-C4-alkoxy-C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, di(C1-C4-alkyl)amino, COR6, phenyl or benzyl, it being possible for the two last-mentioned substituents to be partially or fully halogenated and/or to have attached to them one to three of the following groups:
          •  nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
          • R5 is hydrogen or C1-C4-alkyl;
          • or
          • R4 and R5 together form a C2-C6-alkanediyl chain which can be mono- to tetrasubstituted by C1-C4-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C1-C4-alkyl;
          • or
          • R4 and R9 or R4 and R10 or R5 and R12 or R5 and R13 together form a C2-C6-alkanediyl chain which can be mono- to tetrasubstituted by C1-C4-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C1-C4-alkyl.
      • Also particularly preferred are 3-heterocyclyl-substituted benzoyl derivatives of the formula I where
        • X is S, NR9 or CO
        • or
        • y is O, NR12 or CO.
        • Extraordinarily preferred are 3-heterocyclyl-substituted benzoyl derivatives of the formula I where
          • R4 is halogen, cyano, nitro, C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxycarbonyl-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-cyanoalkyl, C3-C8-cycloalkyl, C1-C6-alkoxy, C1-C4-alkoxy-C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, di(C1-C4-alkyl)amino, COR6, phenyl or benzyl, it being possible for the two last-mentioned substituents to be partially or fully halogenated and/or to have attached to them one to three of the following groups:
          •  nitro, cyano, C1-C4-Alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
          • R5 is hydrogen or C1-C4-alkyl;
          • or
          • R4 and R5 together form a C2-C6-alkanediyl chain which can be mono- to tetrasubstituted by C1-C4-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C1-C4-alkyl;
          • or
          • R4 and R9 or R4 and R10 or R5 and R12 or R5 and R13 together form a C2-C6-alkanediyl chain which can be mono- to tetrasubstituted by C1-C4-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C1-C4-alkyl.


Particularly extraordinarily preferred are the compounds Ia1 ({circumflex over (=)}I where R1═Cl, R2═SO2CH3, R3═H, R16, R18═CH3, Z=H), in particular the compounds of Table 1.










TABLE 1








Ia1




embedded image
















No.
X
R4
R5
Y





Ia1.1
CH2
H
CH3
O


Ia1.2
CH2
H
H
O


Ia1.3
C(CH3)2
H
H
O


Ia1.4
CH2
H
C2H5
O


Ia1.5
CH2
CH3
CH3
O


Ia1.6
CH(CH3)
H
CH3
O


Ia1.7
CH(C2H5)
H
CH3
O


Ia1.8
CH[CH(CH3)2]
H
H
O


Ia1.9
CH2
H
CH(CH3)2
O


Ia1.10
CH(C2H5)
H
C2H5
O










Ia1.11
—CH—(CH2)4—
H
O











Ia1.12
C═O
CH3
CH3
O


Ia1.13
C═O
H
C2H5
O


Ia1.14
C═O
C2H5
C2H5
O


Ia1.15
C═O
H
H
O


Ia1.16
C═O
H
CH3
O


Ia1.17
CH2
H
CH3
S


Ia1.18
C(CH3)2
H
H
S


Ia1.19
CH2
H
C2H5
S


Ia1.20
CH2
CH3
CH3
S


Ia1.21
CH(CH3)
H
CH3
S


Ia1.22
CH(C2H5)
H
CH3
S


Ia1.23
CH(C2H5)
H
C2H5
S










Ia1.24
—CH—(CH2)4—
H
S











Ia1.25
CH[CH(CH3)2]
H
H
S


Ia1.26
CH2
H
CH(CH3)2
S


Ia1.27
CH2
H
CH3
NH


Ia1.28
CH2
H
H
NH


Ia1.29
C(CH3)2
H
H
NH


Ia1.30
CH2
H
C2H5
NH


Ia1.31
CH2
CH3
CH3
NH


Ia1.32
CH(CH3)
H
CH3
NH


Ia1.33
CH(C2H5)
H
CH3
NH


Ia1.34
CH(C2H5)
H
C2H5
NH










Ia1.35
—CH—(CH2)4—
H
NH











Ia1.36
CH[CH(CH3)2]
H
H
NH


Ia1.37
CH2
H
CH(CH3)2
NH


Ia1.38
CH2
H
CH3
NCH3


Ia1.39
CH2
H
H
NCH3


Ia1.40
C(CH3)2
H
H
NCH3


Ia1.41
CH2
H
C2H5
NCH3


Ia1.42
CH2
CH3
CH3
NCH3


Ia1.43
CH(CH3)
H
CH3
NCH3


Ia1.44
CH(C2H5)
H
CH3
NCH3


Ia1.45
CH[CH(CH3)2]
H
H
NCH3


Ia1.46
CH2
H
CH(CH3)2
NCH3


Ia1.47
CH(C2H5)
H
C2H5
NCH3










Ia1.48
—CH—(CH2)4—
H
NCH3











Ia1.49
CH2
H
CH3
NC2H5


Ia1.50
CH2
H
H
NC2H5


Ia1.51
C(CH3)2
H
H
NC2H5


Ia1.52
CH2
H
C2H5
NC2H5


Ia1.53
CH2
CH3
CH3
NC2H5


Ia1.54
CH(CH3)
H
CH3
NC2H5


Ia1.55
CH(C2H5)
H
CH3
NC2H5


Ia1.56
CH[CH(CH3)2]
H
H
NC2H5


Ia1.57
CH2
H
CH(CH3)2
NC2H5


Ia1.58
CH(C2H5)
H
C2H5
NC2H5










Ia1.59
—CH—(CH2)4—
H
NC2H5










Ia1.60
CH2
═O
S


Ia1.61
CH(CH3)
═O
S


Ia1.62
CH(C2H5)
═O
S


Ia1.63
CH[CH(CH3)2]
═O
S


Ia1.64
C(CH3)2
═O
S


Ia1.65
CCH3(C2H5)
═O
S


Ia1.66
CCH3[CH(CH3)2]
═O
S


Ia1.67
CH2
═O
NH


Ia1.68
CH(CH3)
═O
NH


Ia1.69
CH(C2H5)
═O
NH


Ia1.70
CH[CH(CH3)2]
═O
NH


Ia1.71
C(CH3)2
═O
NH


Ia1.72
CCH3(C2H5)
═O
NH


Ia1.73
CCH3[CH(CH3)2]
═O
NH


Ia1.74
CH2
═O
NCH3


Ia1.75
CH(CH3)
═O
NCH3


Ia1.76
CH(C2H5)
═O
NCH3


Ia1.77
CH[CH(CH3)2]
═O
NCH3


Ia1.78
C(CH3)2
═O
NCH3


Ia1.79
CCH3(C2H5)
═O
NCH3


Ia1.80
CCH3[CH(CH3)2]
═O
NCH3











Ia1.81
O
COOCH3
H
CH2


Ia1.82
O
COOC2H5
H
CH2


Ia1.83
O
CONHCH3
H
CH2


Ia1.84
O
CON(CH3)2
H
CH2


Ia1.85
O
CONHC2H5
H
CH2


Ia1.86
O
CON(C2H5)2
H
CH2


Ia1.87
O
CH3
H
CH2


Ia1.88
O
C2H5
H
CH2


Ia1.89
O
CH(CH3)2
H
CH2


Ia1.90
O
COC2H5
H
CH2


Ia1.91
O
CH2CN
H
CH2


Ia1.92
O
CH2N(CH3)2
H
CH2


Ia1.93
O
CH2CN═C(CH3)2
H
CH2


Ia1.94
O
OH(OC2H5)2
H
CH2


Ia1.95
O
OH(OCH3)2
H
CH2


Ia1.96
O
CH3
CH3
CH2


Ia1.97
O
CH3
C2H5
CH2


Ia1.98
O
C2H5
C2H5
CH2










Ia1.99
O
—(CH2)4—
CH2


Ia1.100
O
—(CH2)2—O—(CH2)2—
CH2










Ia1.101
O
H
—(CH2)3—OH—


Ia1.102
O
H
—(CH2)4—OH—











Ia1.103
O
CH3
H
CHCH3










Ia1.104
S
═O
O


Ia1.105
CH2
═S
S


Ia1.106
CH(CH3)
═S
S


Ia1.107
CH(C2H5)
═S
S


Ia1.108
C(CH3)2
═S
S


Ia1.109
O
═O
NH


Ia1.110
O
═O
NCH3











Ia1.111
O
CH3
H
NH


Ia1.112
O
C2H5
H
NH


Ia1.113
O
CH3
CH3
NH


Ia1.114
O
C2H5
C2H5
NH


Ia1.115
O
CH3
H
NCH3


Ia1.116
O
C2H5
H
NCH3


Ia1.117
O
CH3
CH3
NCH3


Ia1.118
O
C2H5
C2H5
NCH3










Ia1.119
NH
═O
NH


Ia1.120
NH
═O
NCH3


Ia1.121
NCH3
═O
NH


Ia1.122
NCH3
═O
NCH3


Ia1.123
NC2H5
═O
NH


Ia1.124
NC2H5
═O
NC2H5









In addition, the following benzoyl derivatives of the formula I are particularly extraordinarily preferred:

    • The compounds Ia2.1-Ia2.124, which differ from the corresponding compounds Ia1.1-Ia1.124 by the fact that R16 is ethyl and R18 is hydrogen.




embedded image


Also particularly extraordinarily preferred are the compounds Ib1 ({circumflex over (=)}I where R1, R2═Cl, R3═H, R16, R18═CH3, Z=H) in particular the compounds of Table 2










TABLE 2








Ib1




embedded image
















No.
X
R4
R5
Y





Ib1.1
CH2
H
CH3
O


Ib1.2
CH2
H
H
O


Ib1.3
C(CH3)2
H
H
O


Ib1.4
CH2
H
C2H5
O


Ib1.5
CH2
CH3
CH3
O


Ib1.6
CH(CH3)
H
CH3
O


Ib1.7
CH(C2H5)
H
CH3
O


Ib1.8
CH[CH(CH3)2]
H
H
O


Ib1.9
CH2
H
CH(CH3)2
O


Ib1.10
CH(C2H5)
H
C2H5
O










Ib1.11
—CH—(CH2)4—
H
O











Ib1.12
C═O
CH3
CH3
O


Ib1.13
C═O
H
C2H5
O


Ib1.14
C═O
C2H5
C2H5
O


Ib1.15
C═O
H
H
O


Ib1.16
C═O
H
CH3
O


Ib1.17
CH2
H
CH3
S


Ib1.18
CH2
H
H
S


Ib1.19
C(CH3)2
H
H
S


Ib1.20
CH2
H
C2H5
S


Ib1.21
CH2
CH3
CH3
S


Ib1.22
CH(CH3)
H
CH3
S


Ib1.23
CH(C2H5)
H
CH3
S


Ib1.24
CH(C2H5)
H
C2H5
S










Ib1.25
—CH—(CH2)4—
H
S











Ib1.26
CH[CH(CH3)2]
H
H
S


Ib1.27
CH2
H
CH(CH3)2
S


Ib1.28
CH2
H
CH3
NH


Ib1.29
CH2
H
H
NH


Ib1.30
C(CH3)2
H
H
NH


Ib1.31
CH2
H
C2H5
NH


Ib1.32
CH2
CH3
CH3
NH


Ib1.33
CH(CH3)
H
CH3
NH


Ib1.34
CH(C2H5)
H
CH3
NH


Ib1.35
CH(C2H5)
H
C2H5
NH










Ib1.36
—CH—(CH2)4—
H
NH











Ib1.37
CH[CH(CH3)2]
H
H
NH


Ib1.38
CH2
H
CH(CH3)2
NH


Ib1.39
CH2
H
CH3
NCH3


Ib1.40
CH2
H
H
NCH3


Ib1.41
C(CH3)2
H
H
NCH3


Ib1.42
CH2
H
C2H5
NCH3


Ib1.43
CH2
CH3
CH3
NCH3


Ib1.44
CH(CH3)
H
CH3
NCH3


Ib1.45
CH(C2H5)
H
CH3
NCH3


Ib1.46
CH[CH(CH3)2]
H
H
NCH3


Ib1.47
CH2
H
CH(CH3)2
NCH3


Ib1.48
CH(C2H5)
H
C2H5
NCH3










Ib1.49
—CH—(CH2)4—
H
NCH3











Ib1.50
CH2
H
CH3
NC2H5


Ib1.51
CH2
H
H
NC2H5


Ib1.52
C(CH3)2
H
H
NC2H5


Ib1.53
CH2
H
C2H5
NC2H5


Ib1.54
CH2
CH3
CH3
NC2H5


Ib1.55
CH(CH3)
H
CH3
NC2H5


Ib1.56
CH(C2H5)
H
CH3
NC2H5


Ib1.57
CH[CH(CH3)2]
H
H
NC2H5


Ib1.58
CH2
H
CH(CH3)2
NC2H5


Ib1.59
CH(C2H5)
H
C2H5
NC2H5










Ib1.60
—CH—(CH2)4—
H
NC2H5










Ib1.61
CH2
═O
S


Ib1.62
CH(CH3)
═O
S


Ib1.63
CH(C2H5)
═O
S


Ib1.64
CH[CH(CH3)2]
═O
S


Ib1.65
C(CH3)2
═O
S


Ib1.66
CCH3(C2H5)
═O
S


Ib1.67
CCH3[CH(CH3)2]
═O
S


Ib1.68
CH2
═O
NH


Ib1.69
CH(CH3)
═O
NH


Ib1.70
CH(C2H5)
═O
NH


Ib1.71
CH[CH(CH3)2]
═O
NH


Ib1.72
C(CH3)2
═O
NH


Ib1.73
CCH3(C2H5)
═O
NH


Ib1.74
CCH3[CH(CH3)2]
═O
NH


Ib1.75
CH2
═O
NCH3


Ib1.76
CH(CH3)
═O
NCH3


Ib1.77
CH(C2H5)
═O
NCH3


Ib1.78
CH[CH(CH3)2]
═O
NCH3


Ib1.79
C(CH3)2
═O
NCH3


Ib1.80
CCH3(C2H5)
═O
NCH3


Ib1.81
CCH3[CH(CH3)2]
═O
NCH3











Ib1.82
O
COOCH3
H
CH2


Ib1.83
O
COOC2H5
H
CH2


Ib1.84
O
CONHCH3
H
CH2


Ib1.85
O
CON(CH3)2
H
CH2


Ib1.86
O
CONHC2H5
H
CH2


Ib1.87
O
CON(C2H5)2
H
CH2


Ib1.88
O
CH3
H
CH2


Ib1.89
O
C2H5
H
CH2


Ib1.90
O
CH(CH3)2
H
CH2


Ib1.91
O
COC2H5
H
CH2


Ib1.92
O
CH2CN
H
CH2


Ib1.93
O
CH2N(CH3)2
H
CH2


Ib1.94
O
CH2CN═C(CH3)2
H
CH2


Ib1.95
O
OH(OC2H5)2
H
CH2


Ib1.96
O
OH(OCH3)2
H
CH2


Ib1.97
O
CH3
CH3
CH2


Ib1.98
O
CH3
C2H5
CH2


Ib1.99
O
C2H5
C2H5
CH2










Ib1.100
O
—(CH2)4—
CH2


Ib1.101
O
—(CH2)2—O—(CH2)2—
CH2










Ib1.102
O
H
—(CH2)3—OH—


Ib1.103
O
H
—(CH2)4—OH—











Ib1.104
O
CH3
H
CHCH3


Ib1.105
O
H
H
CH2










Ib1.106
S
═O
O


Ib1.107
CH2
═S
S


Ib1.108
CH(CH3)
═S
S


Ib1.109
CH(C2H5)
═S
S


Ib1.110
C(CH3)2
═S
S


Ib1.111
O
═O
NH


Ib1.112
O
═O
NCH3











Ib1.113
O
CH3
H
NH


Ib1.114
O
C2H5
H
NH


Ib1.115
O
CH3
CH3
NH


Ib1.116
O
C2H5
C2H5
NH


Ib1.117
O
CH3
H
NCH3


Ib1.118
O
C2H5
H
NCH3


Ib1.119
O
CH3
CH3
NCH3


Ib1.120
O
C2H5
C2H5
NCH3










Ib1.121
NH
═O
NH


Ib1.122
NH
═O
NCH3


Ib1.123
NCH3
═O
NH


Ib1.124
NCH3
═O
NCH3


Ib1.125
NC2H5
═O
NH


Ib1.126
NC2H5
═O
NC2H5









In addition, the following 3-heterocyclyl-substituted benzoyl derivatives of the formula I are particularly extraordinarily preferred:


The compounds Ib2.1-Ib2.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is nitro.




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The compounds Ib3.1-Ib3.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl and R2 is methylsulfonyl.




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The compounds Ib4.1-Ib4.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact R1 is hydrogen and R2 is methylsulfonyl.




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The compounds Ib5.1-Ib5.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is trifluoromethyl and R2 is methylsulfonyl.




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The compounds Ib6.1-Ib6.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl.




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The compounds Ib7.1-Ib7.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro.




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The compounds Ib8.1-Ib8.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is trifluoromethyl.




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The compounds Ib9.1-Ib9.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylthio.




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The compounds Ib10.1-Ib10.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfinyl.




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The compounds Ib11.1-Ib11.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is trifluoromethylsulfonyl.




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The compounds Ib12.1-Ib12.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methoxy and R2 is methylsulfonyl.




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The compounds Ib13.1-Ib13.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is ethylsulfonyl.




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The compounds Ib14.1-Ib14.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact R2 is methylsulfonyl and R3 is methyl.




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The compounds Ib15.1-Ib15.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl and R3 is chlorine.




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The compounds Ib16.1-Ib16.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl and R3 is chlorine.




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The compounds Ib17.1-Ib17.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl and R3 is methyl.




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The compounds Ib18.1-Ib18.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl.




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The compounds Ib19.1-Ib19.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl and R2 is hydrogen.




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The compounds Ib20.1-Ib20.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact R1 is methyl and R2 is nitro.




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The compounds Ib21.1-Ib21.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl and R18 is hydrogen.




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The compounds Ib22.1-Ib22.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is nitro and R18 is hydrogen.




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The compounds Ib23.1-Ib23.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl and R18 is hydrogen.




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The compounds Ib24.1-Ib24.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is hydrogen, R2 is methylsulfonyl and R18 is hydrogen.




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The compounds Ib25.1-Ib25.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is trifluoromethyl, R2 is methylsulfonyl and R18 is hydrogen.




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The compounds Ib26.1-Ib26.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl and R18 is hydrogen.




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The compounds Ib27.1-Ib27.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact R1 is nitro and R18 is hydrogen.




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The compounds Ib28.1-Ib28.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is trifluoromethyl and R18 is hydrogen.




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The compounds Ib29.1-Ib29.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylthio and R18 is hydrogen.




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The compounds Ib30.1-Ib30.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfinyl and R18 is hydrogen.




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The compounds Ib31.1-Ib31.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is trifluoromethylsulfonyl and R18 is hydrogen.




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The compounds Ib32.1-Ib32.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methoxy, R2 is methylsulfonyl and R18 is hydrogen.




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The compounds Ib33.1-Ib33.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is ethylsulfonyl and R18 is hydrogen.




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The compounds Ib34.1-Ib34.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R3 is methyl and R18 is hydrogen.




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The compounds Ib35.1-Ib35.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R3 is chlorine and R18 is hydrogen.




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The compounds Ib36.1-Ib36.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R3 is chlorine and R18 is hydrogen.




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The compounds Ib37.1-Ib37.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R3 is methyl and R18 is hydrogen.




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The compounds Ib38.1-Ib38.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl and R18 is hydrogen.




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The compounds Ib39.1-Ib39.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is hydrogen and R18 is hydrogen.




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The compounds Ib40.1-Ib40.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is nitro and R18 is hydrogen.




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The compounds Ib41.1-Ib41.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is nitro, R16 is ethyl and R18 is hydrogen.




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The compounds Ib42.1-Ib42.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R16 is ethyl and R18 is hydrogen.




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The compounds Ib43.1-Ib43.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is hydrogen, R2 is methylsulfonyl, R16 is ethyl and R18 is hydrogen.




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The compounds Ib44.1-Ib44.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is trifluoromethyl, R2 is methylsulfonyl, R16 is ethyl and R18 is hydrogen.




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The compounds Ib45.1-Ib45.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl, R16 is ethyl and R18 is hydrogen.




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The compounds Ib46.1-Ib46.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro, R16 is ethyl and R18 is hydrogen.




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The compounds Ib47.1-Ib47.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is trifluoromethyl, R16 is ethyl and R18 is hydrogen.




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The compounds Ib48.1-Ib48.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylthio, R16 is ethyl and R18 is hydrogen.




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The compounds Ib49.1-Ib49.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfinyl, R16 is ethyl and R18 is hydrogen.




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The compounds Ib50.1-Ib50.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is trifluoromethylsulfonyl, R16 is ethyl and R18 is hydrogen.




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The compounds Ib51.1-Ib51.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methoxy, R2 is methylsulfonyl, R16 is ethyl and R18 is hydrogen.




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wherein

  • R19 is hydroxyl or C1-C6-alkoxy;
  • R1 is C1-C6-alkyl;
  • R2 is C1-C6-alkylthio or C1-C6-alkylsulfonyl;
  • R3 is hydrogen;
  • R4 and R5 are hydrogen or C1-C4-alkyl;
  • X is CR10R11, wherein R10 and R11 are hydrogen or C1-C4-alkyl, and
  • Y is oxygen.



29. A process for the preparation of the 3-heterocyclyl-substituted benzoyl compound of the formula I defined in claim 28, which comprises acylating a pyrazole of the formula II




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    • with an activated carboxylic acid IIIα or with a carboxylic acid IIIβ







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The compounds Ib52.1-Ib52.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is ethylsulfonyl, R16 is ethyl and R18 is hydrogen.




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The compounds Ib53.1-Ib53.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R3 is methyl, R16 is ethyl and R18 is hydrogen.




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The compounds Ib54.1-Ib54.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R3 is chlorine, R16 is ethyl and R18 is hydrogen.




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The compounds Ib55.1-Ib55.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R3 is chlorine, R16 is ethyl and R18 is hydrogen.




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The compounds Ib56.1-Ib56.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R3 is methyl, R16 is ethyl and R18 is hydrogen.




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The compounds Ib57.1-Ib57.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R16 is ethyl and R18 is hydrogen.




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The compounds Ib58.1-Ib58.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is hydrogen, R16 is ethyl and R18 is hydrogen.




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The compounds Ib59.1-Ib59.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is nitro, R16 is ethyl and R18 is hydrogen.




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The compounds Ib61.1-Ib61.126 [sic], which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R16 is n-propyl and R18 is hydrogen.




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The compounds Ib61.1-Ib61.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is nitro, R16 is n-propyl and R18 is hydrogen.




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The compounds Ib62.1-Ib62.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R16 is n-propyl and R18 is hydrogen.




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The compounds Ib63.1-Ib63.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is hydrogen, R2 is methylsulfonyl, R16 is n-propyl and R18 is hydrogen.




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The compounds Ib64.1-Ib64.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is trifluoromethyl, R2 is methylsulfonyl, R16 is n-propyl and R18 is hydrogen.




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The compounds Ib65.1-Ib65.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl, R16 is n-propyl and R18 is hydrogen.




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The compounds Ib66.1-Ib66.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro, R16 is n-propyl and R18 is hydrogen.




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The compounds Ib67.1-Ib67.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is trifluoromethyl, R16 is n-propyl and R18 is hydrogen.




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The compounds Ib68.1-Ib68.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylthio, R16 is n-propyl and R18 is hydrogen.




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The compounds Ib69.1-Ib69.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfinyl, R16 is n-propyl and R18 is hydrogen.




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The compounds Ib70.1-Ib70.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is trifluoromethylsulfonyl, R16 is n-propyl and R18 is hydrogen.




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The compounds Ib71.1-Ib71.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methoxy, R2 is methylsulfonyl, R16 is n-propyl and R18 is hydrogen.




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The compounds Ib72.1-Ib72.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is ethylsulfonyl, R16 is n-propyl and R18 is hydrogen.




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The compounds Ib73.1-Ib73.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R3 is methyl, R16 is n-propyl and R18 is hydrogen.




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The compounds Ib74.1-Ib74.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R3 is chlorine, R16 is n-propyl and R18 is hydrogen.




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The compounds Ib75.1-Ib75.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R3 is chlorine, R16 is n-propyl and R8 is hydrogen.




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The compounds Ib76.1-Ib76.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R3 is methyl, R6 is n-propyl and R18 is hydrogen.




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The compounds Ib77.1-Ib77.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R16 is n-propyl and R18 is hydrogen.




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The compounds Ib78.1-Ib78.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is hydrogen, R16 is n-propyl and R18 is hydrogen.




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The compounds Ib79.1-Ib79.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is nitro, R16 is n-propyl and R18 is hydrogen.




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The compounds Ib80.1-Ib80.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R16 is n-propyl and R18 is hydrogen.




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The compounds Ib81.1-Ib81.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib82.1-Ib82.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is nitro, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib83.1-Ib83.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib84.1-Ib84.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is hydrogen, R2 is methylsulfonyl, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib85.1-Ib85.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is trifluoromethyl, R2 is methylsulfonyl, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib86.1-Ib86.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib87.1-Ib87.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib88.1-Ib88.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is trifluoromethyl, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib89.1-Ib89.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylthio, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib90.1-Ib90.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfinyl, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib91.1-Ib91.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is trifluoromethylsulfonyl, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib92.1-Ib92.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methoxy, R2 is methylsulfonyl, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib93.1-Ib93.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is ethylsulfonyl, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib94.1-Ib94.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R3 is methyl, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib95.1-Ib95.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R3 is chlorine, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib96.1-Ib96.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R3 is chlorine, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib97.1Ib97.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R3 is methyl, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib98.1-Ib98.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib99.1-Ib99.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is hydrogen, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib100.1-Ib100.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is nitro, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib101.1-Ib101.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R16 is n-butyl and R18 is hydrogen.




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The compounds Ib102.1-Ib102.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R16 is iso-butyl and R18 is hydrogen.




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The compounds Ib103.11-b103.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is nitro, R16 is iso butyl and R18 is hydrogen.




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The compounds Ib104.1-b104.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R16 is iso-butyl and R18 is hydrogen.




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The compounds Ib105.1-Ib105.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is hydrogen, R2 is methylsulfonyl, R16 is iso-butyl and R18 is hydrogen.




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The compounds Ib106.1-Ib106.126, which differ from the corresponding compounds Tb1.1-Ib1.126 by the fact that R1 is trifluoromethyl, R2 is methylsulfonyl, R16 is iso-butyl and R18 is hydrogen.




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The compounds Ib107.1-Ib107.126, which differ from the corresponding compounds Ib1.1Ib1.126 by the fact that R1 is methylsulfonyl, R16 is iso-butyl and R18 is hydrogen.




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The compounds Ib108.1-Ib108.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro, R16 is iso-butyl and R18 is hydrogen.




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The compounds Ib109.1-Ib109.126, which differ from the corresponding compounds Ib1.1-Ibl1.126 by the fact that R2 is trifluoromethyl, R16 is iso-butyl and R18 is hydrogen.




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The compounds Ib110.1Ib110.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylthio, R6 is iso-butyl and R18 is hydrogen.




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The compounds Ib111.1-Ib111.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfinyl, R16 is iso-butyl and R18 is hydrogen.




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The compounds Ib112.1-Ib112.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is trifluoromethylsulfonyl, R16 is iso-butyl and R18 is hydrogen.




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The compounds Ib114.1-Ib114.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methoxy, R2 is methylsulfonyl, R16 is iso-butyl and R18 is hydrogen.




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The compounds Ib114.11b114.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is ethylsulfonyl, R16 is iso-butyl and R 18 is hydrogen.




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The compounds Ib115.1-Ib115.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R3 is methyl, R16 is iso-butyl and R18 is hydrogen.




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The compounds Ib116.1-Ib116.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R3 is chlorine, R16 is iso-butyl and R18 is hydrogen.




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The compounds Ib117.1-Ib117.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R3 is chlorine, R16 is iso-butyl and R18 is hydrogen.




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The compounds Ib118.1-Ib118.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R3 is methyl, R16 is iso-butyl and R18 is hydrogen.




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The compounds Ib119.1-Ib119.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R16 is iso-butyl and R18 is hydrogen.




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The compounds Ib120.1-Ib120.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is hydrogen, R16 is iso-butyl and R18 is hydrogen.




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The compounds Ib121.1-Ib121.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is nitro, R16 is iso-butyl and R18 is hydrogen.




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The compounds Ib122.1-Ib122.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R16 is iso-butyl and R18 is hydrogen.




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The compounds Ib123.1-Ib123.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact R1 is methylsulfonyl and R2 is trifluoromethyl.




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The compounds Ib124.1-Ib124.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl, R2 is trifluoromethyl, and R18 is hydrogen.




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The compounds Ib125.1-Ib125.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl, R2 is trifluoromethyl, R16 is n-propyl and R18 is hydrogen.




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The compounds Ib126.1-Ib126.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl, R2 is trifluoromethyl, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib127.1-Ib127.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl, R2 is trifluoromethyl, R16 is iso-butyl and R18 is hydrogen.




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The compounds Ib128.1-Ib128.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl, R2 is trifluoromethyl, R16 is ethyl and R18 is hydrogen.




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The compounds Ib129.1-Ib129.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro and R2 is methylsulfonyl.




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The compounds Ib130.1-Ib130.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro, R2 is methylsulfonyl and R18 is hydrogen.




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The compounds Ib131.1-Ib131.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro, R2 is methylsulfonyl, R16 is n-propyl and R18 is hydrogen.




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The compounds Ib132.1-Ib132.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro, R2 is methylsulfonyl, R16 is n-butyl and R18 is hydrogen.




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The compounds Ib133.1-Ib133.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro, R2 is methylsulfonyl, R16 is iso-butyl and R18 is hydrogen.




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The compounds Ib134.1-Ib134.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro, R2 is methylsulfonyl, R16 is ethyl and R18 is hydrogen.




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The compounds Ib135.1-Ib135.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R18 is hydrogen.




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The compounds Ib136.1-Ib136.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R16 is ethyl and R18 is hydrogen.




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The compounds Ib137.1-Ib137.126 which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that Z is methylsulfonyl and R18 is hydrogen.




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The compounds Ib138.1-Ib138.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, Z is methylsulfonyl and R18 is hydrogen.




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The compounds Ib139.1-Ib139.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is nitro, Z is methylsulfonyl and R18 is hydrogen.




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The compounds Ib140.1-Ib140.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, Z is methylsulfonyl and R18 is hydrogen.




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The compounds Ib141.1-Ib141.126 which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl, Z is methylsulfonyl and R18 is hydrogen.




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The compounds Ib142.1-Ib142.126 which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro, Z is methylsulfonyl and R18 is hydrogen.




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The compounds Ib143.1-Ib143.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact R1 is methoxy, R2 and Z are methylsulfonyl and R18 is hydrogen.




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The compounds Ib144.1-Ib144.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is ethylsulfonyl, Z is methylsulfonyl and R18 is hydrogen.




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The compounds Ib145.1-Ib145.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R16 is ethyl, Z is methylsulfonyl and R18 is hydrogen.




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The compounds Ib146.1-Ib146.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R16 is ethyl, Z is methylsulfonyl and R18 is hydrogen.




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The compounds Ib147.1-Ib147.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is nitro, R16 is ethyl, Z is methylsulfonyl and R18 is hydrogen.




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The compounds Ib148.1-Ib148.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R16 is ethyl, Z is methylsulfonyl and R18 is hydrogen.




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The compounds Ib149.1-Ib149.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl, R16 is ethyl, Z is methylsulfonyl and R18 is hydrogen.




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The compounds Ib150.1-Ib150.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro, R16 is ethyl, Z is methylsulfonyl and R18 is hydrogen.




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The compounds Ib151.1-Ib151.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methoxy, R2 is methylsulfonyl, R16 is ethyl, Z is methylsulfonyl and R18 is hydrogen.




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The compounds Ib152.1-Ib152.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is ethylsulfonyl, R16 is ethyl, Z is methylsulfonyl and R18 is hydrogen.




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The compounds Ib153.1-Ib153.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that Z is methylsulfonyl.




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The compounds Ib154.1-Ib154.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 and Z are methylsulfonyl.




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The compounds Ib155.1-Ib155.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is nitro and Z is methylsulfonyl.




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The compounds Ib156.1-Ib156.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 and Z are methylsulfonyl.




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The compounds Ib157.1-Ib157.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 and Z are methylsulfonyl.




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The compounds Ib158.1-Ib158.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro and Z is methylsulfonyl.




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The compounds Ib159.1-Ib159.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methoxy, R2 and Z are methylsulfonyl.




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The compounds Ib160.1-Ib160.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is ethylsulfonyl and Z is methylsulfonyl.




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The compounds Ib161.1-Ib161.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that Z is ethylsulfonyl and R18 is hydrogen.




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The compounds Ib162.1-Ib162.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, Z is ethylsulfonyl and R18 is hydrogen.




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The compounds Ib163.1-Ib163.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is nitro, Z is ethylsulfonyl and R18 is hydrogen.




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The compounds Ib164.1-Ib164.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, Z is ethylsulfonyl and R18 is hydrogen.




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The compounds Ib165.1-Ib165.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl, Z is ethylsulfonyl and R18 is hydrogen.




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The compounds Ib166.1-Ib166.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro, Z is ethylsulfonyl and R18 is hydrogen.




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The compounds Ib167.1-Ib167.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methoxy, R2 is methylsulfonyl, Z is ethylsulfonyl and R18 is hydrogen.




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The compounds Ib168.1-Ib168.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 and Z are ethylsulfonyl and R18 is hydrogen.




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The compounds Ib169.1-Ib169.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R16 is ethyl, Z is ethylsulfonyl and R18 is hydrogen.




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The compounds Ib170.1-Ib170.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R16 is ethyl, Z is ethylsulfonyl and R18 is hydrogen.




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The compounds Ib171.1-Ib171.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is nitro, R16 is ethyl, Z is ethylsulfonyl and R18 is hydrogen.




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The compounds Ib172.1-Ib172.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R16 is ethyl, Z is ethylsulfonyl and R18 is hydrogen.




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The compounds Ib173.1-Ib173.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl, R16 is ethyl, Z is ethylsulfonyl and R18 is hydrogen.




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The compounds Ib174.1-Ib174.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro, R16 is ethyl, Z is ethylsulfonyl and R18 is hydrogen.




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The compounds Ib175.1-Ib175.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methoxy, R2 is methylsulfonyl, R16 is ethyl, Z is ethylsulfonyl and R18 is hydrogen.




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The compounds Ib176.1-Ib176.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is ethylsulfonyl, R16 is ethyl, Z is ethylsulfonyl and R18 is hydrogen.




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The compounds Ib177.1-Ib177.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that Z is ethylsulfonyl.




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The compounds Ib178.1-Ib178.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl and Z is ethylsulfonyl.




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The compounds Ib179.1-Ib179.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is nitro and Z is ethylsulfonyl.




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The compounds Ib180.1-Ib180.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl and Z is ethylsulfonyl.




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The compounds Ib181.1-Ib181.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl and Z is ethylsulfonyl.




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The compounds Ib182.1-Ib182.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro and Z is ethylsulfonyl.




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The compounds Ib183.1-Ib183.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methoxy, R2 is methylsulfonyl and Z is ethylsulfonyl.




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The compounds Ib184.1-Ib184.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 and Z are ethylsulfonyl.




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The compounds Ib185.1-Ib185.126 which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that Z is iso-propylsulfonyl and R18 is hydrogen.




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The compounds Ib186.1-Ib186.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, Z is iso-propylsulfonyl and R18 is hydrogen.




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The compounds Ib187.1-Ib187.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is nitro, Z is iso-propylsulfonyl and R18 is hydrogen.




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The compounds Ib188.1-Ib188.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, Z is iso-propylsulfonyl and R18 is hydrogen.




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The compounds Ib189.1-Ib189.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl, Z is iso-propylsulfonyl and R18 is hydrogen.




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The compounds Ib190.1-Ib190.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro, Z is iso-propylsulfonyl and R18 is hydrogen.




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The compounds Ib191.1-Ib191.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methoxy, R2 is methylsulfonyl, Z is iso-propylsulfonyl and R18 is hydrogen.




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The compounds Ib192.1-Ib192.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is ethylsulfonyl, Z is isopropylsulfonyl and R18 is hydrogen.




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The compounds Ib193.1-Ib193.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R16 is ethyl, Z is iso-propylsulfonyl and R18 is hydrogen.




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The compounds Ib194.1-Ib194.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R16 is ethyl, Z is iso-propylsulfonyl and R18 is hydrogen.




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The compounds Ib195.1-Ib195.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is nitro, R16 is ethyl, Z is iso-propylsulfonyl and R18 is hydrogen.




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The compounds Ib196.1-Ib196.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R16 is ethyl, Z is iso-propylsulfonyl and R18 is hydrogen.




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The compounds Ib197.1-Ib197.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl, R16 is ethyl, Z is iso-propylsulfonyl and R18 is hydrogen.




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The compounds Ib198.1-Ib198.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro, R16 is ethyl, Z is iso-propylsulfonyl and R18 is hydrogen.




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The compounds Ib199.1-Ib199.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methoxy, R2 is methylsulfonyl, R16 is ethyl, Z is iso-propylsulfonyl and R18 is hydrogen.




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The compounds Ib200.1-Ib200.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is ethylsulfonyl, R16 is ethyl, Z is iso-propylsulfonyl and R18 is hydrogen.




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The compounds Ib201.1-Ib201.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that Z is n-propylsulfonyl and R18 is hydrogen.




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The compounds Ib202.1-Ib202.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, Z is n-propylsulfonyl and R18 is hydrogen.




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The compounds Ib203.1-Ib203.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is nitro, Z is n-propylsulfonyl and R18 is hydrogen.




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The compounds Ib204.1-Ib204.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, Z is n-propylsulfonyl and R18 is hydrogen.




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The compounds Ib205.1-Ib205.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl, Z is n-propylsulfonyl and R18 is hydrogen.




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The compounds Ib206.1-Ib206.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro, Z is n-propylsulfonyl and R18 is hydrogen.




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The compounds Ib207.1-Ib207.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methoxy, R2 is methylsulfonyl, Z is n-propylsulfonyl and R18 is hydrogen.




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The compounds Ib.208.1-Ib208.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is ethylsulfonyl, Z is n-propylsulfonyl and R18 is hydrogen.




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The compounds Ib209.1-Ib209.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R16 is ethyl, Z is n-propylsulfonyl and R18 is hydrogen.




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The compounds Ib210.1-Ib210.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R16 is ethyl, Z is n-propylsulfonyl and R18 is hydrogen.




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The compounds Ib211.1-211.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is nitro, R16 is ethyl, Z is n-propylsulfonyl and R18 is hydrogen.




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The compounds Ib212.1-Ib212.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R16 is ethyl, Z is n-propylsulfonyl and R18 is hydrogen.




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The compounds Ib213.1-Ib213.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl, R16 is ethyl, Z is n-propylsulfonyl and R18 is hydrogen.




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The compounds Ib214.1-Ib214.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro, R16 is ethyl, Z is n-propylsulfonyl and R18 is hydrogen.




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The compounds Ib215.1-Ib215.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methoxy, R2 is methylsulfonyl, R16 is ethyl, Z is n-propylsulfonyl and R18 is hydrogen.




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The compounds Ib216.1-Ib216.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is ethylsulfonyl, R16 is ethyl, Z is n-propylsulfonyl and R18 is hydrogen.




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The compounds Ib217.1-Ib217.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that Z is n-butylsulfonyl and R18 is hydrogen.




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The compounds Ib218.1-Ib218.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, Z is n-butylsulfonyl and R18 is hydrogen.




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The compounds Ib219.1-Ib219.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is nitro, Z is n-butylsulfonyl and R18 is hydrogen.




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The compounds Ib220.1-Ib220.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, Z is n-butylsulfonyl and R18 is hydrogen.




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The compounds Ib221.1-Ib221.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl, Z is n-butylsulfonyl and R18 is hydrogen.




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The compounds Ib222.1-Ib222.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro, Z is n-butylsulfonyl and R18 is hydrogen.




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The compounds Ib223.1-Ib223.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methoxy, R2 is methylsulfonyl, Z is n-butylsulfonyl and R18 is hydrogen.




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The compounds Ib224.1-Ib224.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is ethylsulfonyl, Z is n-butylsulfonyl and R18 is hydrogen.




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The compounds Ib225.1-Ib225.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R16 is ethyl, Z is n-butylsulfonyl and R18 is hydrogen.




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The compounds Ib226.1-Ib226.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R16 is ethyl, Z is n-butylsulfonyl and R18 is hydrogen.




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The compounds Ib227.1-Ib227.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is nitro, R16 is ethyl, Z is n-butylsulfonyl and R18 is hydrogen.




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The compounds Ib228.1-Ib228.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R16 is ethyl, Z is n-butylsulfonyl and R18 is hydrogen.




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The compounds Ib229.1-Ib229.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl, R16 is ethyl, Z is n-butylsulfonyl and R18 is hydrogen.




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The compounds Ib230.1-Ib230.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro, R16 is ethyl, Z is n-butylsulfonyl and R18 is hydrogen.




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The compounds Ib231.1-Ib231.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methoxy, R2 is methylsulfonyl, R16 is ethyl, Z is n-butylsulfonyl and R18 is hydrogen.




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The compounds Ib232.1-Ib232.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is ethylsulfonyl, R16 is ethyl, Z is n-butylsulfonyl and R18 is hydrogen.




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The compounds Ib233.1-Ib233.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that Z is iso-butylsulfonyl and R18 is hydrogen.




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The compounds Ib234.1-Ib234.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, Z is iso-butylsulfonyl and R18 is hydrogen.




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The compounds Ib235.1-Ib235.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is nitro, Z is iso-butylsulfonyl and R18 is hydrogen.




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The compounds Ib236.1-Ib236.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, Z is iso-butylsulfonyl and R18 is hydrogen.




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The compounds Ib237.1-Ib237.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl, Z is iso-butylsulfonyl and R18 is hydrogen.




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The compounds Ib238.1-Ib238.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro, Z is iso-butylsulfonyl and R18 is hydrogen.




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The compounds Ib239.1-Ib239.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methoxy, R2 is methylsulfonyl, Z is iso-butylsulfonyl and R18 is hydrogen.




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The compounds Ib240.1-Ib240.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is ethylsulfonyl, Z is iso-butylsulfonyl and R18 is hydrogen.




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The compounds Ib241.1-Ib241.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R16 is ethyl, Z is iso-butylsulfonyl and R18 is hydrogen.




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The compounds Ib242.1-Ib242.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R16 is ethyl, Z is iso-butylsulfonyl and R18 is hydrogen.




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The compounds Ib243.1-Ib243.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is nitro, R16 is ethyl, Z is iso-butylsulfonyl and R18 is hydrogen.




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The compounds Ib244.1-Ib244.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R16 is ethyl, Z is iso-butylsulfonyl and R18 is hydrogen.




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The compounds Ib245.1-Ib245.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methylsulfonyl, R16 is ethyl, Z is iso-butylsulfonyl and R18 is hydrogen.




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The compounds Ib246.1-Ib246.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is nitro, R16 is ethyl, Z is iso-butylsulfonyl and R18 is hydrogen.




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The compounds Ib247.1-Ib247.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methoxy, R2 is methylsulfonyl, R16 is ethyl, Z is iso-butylsulfonyl and R18 is hydrogen.




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The compounds Ib248.1-Ib248.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R16 is ethyl, Z is iso-butylsulfonyl and R18 is hydrogen.




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The compounds Ib249.1-Ib249.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that Z is phenylsulfonyl and R18 is hydrogen.




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The compounds Ib250.1-Ib250.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, Z is phenylsulfonyl and R18 is hydrogen.




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The compounds Ib251.1-Ib251.126 which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, Z is phenylsulfonyl and R18 is hydrogen.




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The compounds Ib252.1-Ib252.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is ethylsulfonyl, Z is phenylsulfonyl and R18 is hydrogen.




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The compounds Ib253.1-Ib253.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R16 is ethyl, Z is phenylsulfonyl and R18 is hydrogen.




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The compounds Ib254.1-Ib254.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R16 is ethyl, Z is phenylsulfonyl and R18 is hydrogen.




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The compounds Ib255.1-Ib255.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R16 is ethyl, Z is phenylsulfonyl and R18 is hydrogen.




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The compounds Ib256.1-Ib256.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is ethylsulfonyl, R16 is ethyl, Z is phenylsulfonyl and R18 is hydrogen.




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The compounds Ib257.1-Ib257.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that Z is p-toluenesulfonyl and R18 is hydrogen.




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The compounds Ib258.1-Ib258.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, Z is p-toluenesulfonyl and R18 is hydrogen.




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The compounds Ib259.1-Ib259.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, Z is p-toluenesulfonyl and R18 is hydrogen.




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The compounds Ib260.1-Ib260.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is ethylsulfonyl, Z is p-toluenesulfonyl and R18 is hydrogen.




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The compounds Ib261.1-Ib261.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R16 is ethyl, Z is p-toluenesulfonyl and R18 is hydrogen.




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The compounds Ib262.1-Ib262.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is methylsulfonyl, R16 is ethyl, Z is p-toluenesulfonyl and R18 is hydrogen.




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The compounds Ib263.1-Ib263.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R1 is methyl, R2 is methylsulfonyl, R16 is ethyl, Z is p-toluenesulfonyl and R18 is hydrogen.




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The compounds Ib264-Ib264.126, which differ from the corresponding compounds Ib1.1-Ib1.126 by the fact that R2 is ethylsulfonyl, R16 is ethyl, Z is p-toluenesulfonyl and R18 is hydrogen.




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Also particularly preferred are 3-heterocyclyl-substituted benzoyl derivatives of the formula I where:

  • R1 is halogen, C1-C6-alkyl, C1-C6-alkylthio or C1-C6-alkylsulfonyl;
    • in particular chlorine, methyl, methylthio or methylsulfonyl;
  • R2 is hydrogen, nitro, halogen, C1-C6-alkylthio, C1-C6-alkylsulfinyl or C1-C6-alkylsulfonyl;
    • in particular hydrogen, nitro, chlorine, methylthio, methylsulfinyl, methylsulfonyl, ethylsulfonyl or propylsulfonyl;
  • R3 is hydrogen;
  • R4, R5 are hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-alkylthio or COR6;
    • in particular hydrogen, fluorine, methyl, ethyl, propyl, trifluoromethyl, chloromethyl, 1-chloroeth-1-yl, methoxy, ethoxy, ethylthio or ethoxycarbonyl;


      or
  • R4 and R5 together form a C2-C6-alkanediyl chain which can be mono- to polysubstituted by C1-C4-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted [lacuna] C1-C4-alkyl;
  • R6 is C1-C4-alkoxy;
    • in particular ethyl;
  • X is O or CR10R11;
  • Y is O, S or CR13R14;
  • R10, R11, R13, R14 are hydrogen, C1-C4-alkyl or C1-C4-haloalkyl; in particular hydrogen, methyl or chloromethyl;


    or
  • R5 and R13 together form a C2-C6-alkanediyl chain which can be mono- to polysubstituted by C1-C4-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted [lacuna] C1-C4-alkyl; in particular 1,3-propdiyl [sic];
  • R16 is C1-C6-alkyl;
    • in particular methyl, ethyl, propyl, 2-methylpropyl or butyl;
  • Z is H or SO2R17;
  • R17 is C1-C4-alkyl;
    • in particular methyl, ethyl, propyl or 2-methylpropyl;


with the exception of 4-[2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]-1-ethyl-5-hydroxy-1H-pyrazole, 4-[2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-1,3-dimethyl-5-hydroxy-1H-pyrazole, 4-[2-chloro-3-(5-cyano-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]-1,3-dimethyl-5-hydroxy-1H-pyrazole and 4-[2-chloro-3-(4,5-dihydrothiazol-2-yl)-4-methylsulfonylbenzoyl]-1,3-dimethyl-5-hydroxy-1H-pyrazole;


and the agriculturally useful salts thereof;


in particular alkali metal salts and ammonium salts.


The 3-heterocyclyl-substituted benzoyl derivatives of the formula I are obtainable by various routes, for example by the following process:


Process A:


Reaction of pyrazoles of the formula II (where Z=H) with an activated benzoic acid IIIα or a benxoic acid IIIβ, which is preferably activated in situ to give the acylating product and subsequently subjecting the latter to a rearrangement reaction.




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L1 is a nucleophilically displaceable leaving group such as halogen, eg. bromine, chlorine, hetaryl, eg. imidazolyl, pyridyl, carboxylate, eg. acetate, trifluoroacetate, and the like.


The activated benzoic acid can be employed directly, as in the case of the benzoyl halides, or it can be prepared in situ, for example with dicyclohexylcarbodiimide, triphenylphosphine/azodicarboxylic ester, 2-pyridine disulfide/triphenylphosphine, carbonyldiimidazole and the like.


It may be advantageous to carry out the acylation reaction in the presence of a base. The reactants and the auxiliary base are expediently employed in equimolar amounts. A small excess of the auxiliary base, for example 1.2 to 1.5 mol equivalents based on II, may be advantageous under certain circumstances.


Suitable auxiliary bases are tertiary alkylamines, pyridine or alkali metal carbonates. Examples of solvents which can be used are chlorinated hydrocarbons such as methylene chloride, 1,2-dichloroethane, aromatic hydrocarbons such as toluene, xylene, chlorobenzene, ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane, polar aprotic solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide, or esters such as ethyl acetate, or mixtures of these.


If benzoyl halides are employed as activated carboxylic acid component, it may be expedient to cool the reaction mixture to 0-10° C. when adding this reactant. The mixture is subsequently stirred at 20-100° C., preferably at 25-50° C., until the reaction is complete. Work-up is carried out in the customary manner, for example the reaction mixture is poured into water and the product of value is extracted. Especially suitable solvents for this purpose are methylene chloride, diethyl ether and ethyl acetate. After the organic phase has been dried and the solvent removed, the crude ester can be employed without further purification for the rearrangement reaction.


Rearrangement of the esters to give the compounds of the formula I is expediently carried out at from 20 to 40° C. in a solvent and in the presence of a base and, if appropriate, with the aid of a cyano compound as catalyst.


Examples of solvents which can be used are acetonitrile, methylene chloride, 1,2-dichlorethane, dioxane, ethyl acetate, toluene or mixtures of these. Preferred solvents are acetonitrile and dioxane.


Suitable bases are tertiary amines such triethylamine, pyridine, or alkali metal carbonates such as sodium carbonate, potassium carbonate, all of which are preferably employed in equimolar amounts or up to a fourfold excess, based on the ester. Triethylamine or alkali metal carbonate are preferably used, but by preference in a ratio of twice the equimolar amount based on the ester.


Suitable cyano compounds are inorganic cyanides such as sodium cyanide, potassium cyanide, and organic cyano compounds such as acetone cyanohydrin, trimethylsily cyanide. They are employed in an amount of from 1 to 50 mol percent, based on the ester. Substances which are preferably employed are acetone cyanohydrin or trimethylsilyl cyanide, for example in an amount of from 5 to 15, preferably 10, mol percent, based on the ester.


Work-up can be effected in a manner known per se. For example, the reaction mixture is acidified with dilute mineral acid, such as 5% strength hydrochloric acid or sulfuric acid, and extracted with an organic solvent, eg. methylene chloride or ethyl acetate. The organic extract can be extracted with 5-10% strength alkali metal carbonate solution, eg. sodium carbonate or potassium carbonate solution. The aqueous phase is acidified, and the precipitate which forms is filtered off with suction and/or extracted with methylene chloride or ethyl acetate, dried and concentrated. (Examples of the synthesis of esters from hydroxypyrazoles and of the rearrangement of the esters are mentioned, for example, in EP-A 282 944 and U.S. Pat. No. 4,643,757).


Process B:


Reaction of 3-heterocyclyl-substituted benzoyl derivatives of the formula I (where Z=H) with a compound of the formula V (where Z=SO2R17)




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L2 is a nucleophilically displaceable leaving group, such as halogen, eg. bromine, chlorine, hetaryl, eg. imidazolyl, pyridyl, sulfonate, eg. OSO2R17.


The compounds of the formula V can be employed directly such as, for example, in the case of the sulfonyl halides or sulfonic anhydrides, or they can be prepared in situ, for example activated sulfonic acids (by means of sulfonic acid and dicyclohexylcarbodiimide, carbonyldiimidazole and the like).


As a rule, the starting compounds are employed in an equimolar ratio. However, it may also be advantageous to employ an excess of one or the other component.


It may be advantageous to carry out the reaction in the presence of a base. The reactants and the auxiliary base are expediently employed in equimolar ratios. An excess of the auxiliary base, for example 1.5 to 3 mol equivalents, based on II, may be advantageous under certain circumstances.


Suitable auxiliary bases are tertiary alkylamines such as triethylamine or pyridine, alkali metal carbonates, eg. sodium carbonate or potassium carbonate, and alkali metal hydrides, eg. sodium hydride. Triethylamine and pyridine are preferably used.


Examples of suitable solvents are chlorinated hydrocarbons such as methylene chloride or 1,2-dichlorethane, aromatic hydrocarbons, eg. toluene, xylene or chlorobenzene, ethers such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran or dioxane, polar aprotic solvents such as acetonitrile, dimethylformamide or dimethyl sulfoxide, or esters such as ethyl acetate, or mixtures of these.


As a rule, the reaction temperature is in the range of from 0° C. to the boiling point of the reaction mixture.


Work-up can be effected in a manner known per se to give the product.


Those pyrazoles of the formula II (where Z=H) which are used as starting materials and which are not already known can be prepared by processes known per se (for example EP-A 240 001 and J. Prakt. Chem. 315, 383 (1973)).


Novel 3-heterocyclyl-substituted benzoic acid derivatives of the formula III




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are those where the variables have the following meanings:

  • R1, R2 are hydrogen, nitro, halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C6-alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6-alkylsulfonyl or C1-C6-haloalkylsulfonyl;
  • R3 is hydrogen, halogen or C1-C6-alkyl;
  • R4, R5 are hydrogen, halogen, cyano, nitro, C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, di(C1-C4-alkoxy)-C1-C4-alkyl, di(C1-C4-alkyl)amino-C1-C4-alkyl, [2,2-di(C1-C4-alkyl)hydrazino-1]-C1-C4-alkyl, C1-C6-alkyliminooxy-C1-C4-alkyl, C1-C4-alkoxycarbonyl-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-cyanoalkyl, C3-C8-cycloalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C2-C4-alkoxy, C1-C4-haloalkoxy, hydroxyl, C1-C4-alkylcarbonyloxy, C1-C4-alkylthio, C1-C4-haloalkylthio, di(C1-C4-alkyl)amino, COR6, phenyl or benzyl, it being possible for the two last-mentioned substituents to be partially or fully halogenated and/or to have attached to them one to three of the following groups: nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;


    or
  • R4 and R5 together form a C2-C6-alkanediyl chain which can be mono- to tetrasubstituted by C1-C4-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C1-C4-alkyl;


    or
  • R4 and R5 together with the corresponding carbon form a carbonyl or a thiocarbonyl group;
  • R6 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C2-C4-alkoxy, C1-C4-haloalkoxy, C3-C6-alkenyloxy, C3-C6-alkynyloxy or NR7R8;
  • R7 is hydrogen or C1-C4-alkyl;
  • R8 is C1-C4-alkyl;
  • X is O, S, NR9, CO or CR10R11;
  • Y Y is O, S, NR12, CO or CR13R14;
  • R9, R12 are hydrogen or C1-C4-alkyl;
  • R10, R11, R13, R14 are hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxycarbonyl, C1-C4-haloalkoxycarbonyl or CONR7R8;


    or
  • R4 and R9 or R4 and R10 or R5 and R12 or R5 and R13 together form a C2-C6-alkanediyl chain which can be mono- to tetrasubstituted by C1-C4-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C1-C4-alkyl;
  • R19 is hydroxyl or a radical which can be removed by hydrolysis;


with the exception of methyl 2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoate, methyl 2-chloro-3-(4,5-dihydrooxazol-2-yl)-4-methylsulfonylbenzoate and methyl 2,4-dichloro-3-(5-methylcarbonyloxy-4,5-dihydroisoxazol-3-yl)-benzoate.


Examples of radicals which can be removed by hydrolysis are alkoxy, phenoxy, alkylthio and phenylthio radicals which are unsubstituted or substituted, halides, hetaryl radicals which are bonded via nitrogen; amino, imino radicals which are unsubstituted or substituted, and the like.


Preferred are 3-heterocyclyl-substituted benzoic acid halides of the formula IIIα′, where L1′=halogen ({circumflex over (=)}III where R19=halogen)




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where the variables R1 to R5, X and Y have the meanings given under the formula III and

  • L1′ is halogen, in particular chlorine or bromine.


Equally preferred are 3-heterocyclyl-substituted benzoic acids of the formula IIIβ ({circumflex over (=)}III where R19=hydroxyl)




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where the variables R1 to R5, X and Y have the meanings given under formula III.


Equally preferred are 3-heterocyclyl-substituted benzoic esters of the formula IIIγ ({circumflex over (=)}III where R19═C1-C6-alkoxy)




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where the variables R1 to R5, X and Y have the meanings given under formula III and

  • L3 is C1-C6-alkoxy.


The specially preferred embodiments of the 3-heteroacyclyl-substituted benzoic acid derivatives of the formula III with regard to the variables R1 to R5, X and Y correspond to those of the 3-heterocyclyl-substituted benzoyl derivatives of the formula I.


Also preferred are 3-heterocyclyl-substituted benzoic acid derivatives of the formula III, where:

  • R1 is halogen, C1-C6-alkyl, C1-C6-alkylthio or C1-C6-alkylsulfonyl;
    • in particular chlorine, methyl, methylthio or methylsulfonyl;
    • extraordinarily preferably chlorine;
  • R2 is hydrogen, nitro, halogen, C1-C6-alkylthio, C1-C6-alkylsulfinyl or C1-C6-alkylsulfonyl;
    • in particular hydrogen, nitro, chlorine, methylthio, methylsulfinyl, methylsulfonyl, ethylsulfonyl or propylsulfonyl;
    • extraordinarily preferably hydrogen, chlorine, methylthio, methylsulfonyl, ethylsulfonyl or propylsulfonyl;
  • R3 is hydrogen;
  • R4, R5 are hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, hydroxyl, C1-C4-alkylcarbonyloxy, C1-C4-alkylthio or COR6;
    • in particular hydrogen, fluorine, methyl, ethyl, propyl, trifluoromethyl, chloromethyl, 2-chloroeth-1-yl, methoxy, ethoxy, 2-methylprop-1-oxy, hydroxyl, methylcarbonyloxy, ethylthio, formyl, methylcarbonyl, methoxycarbonyl or ethoxycarbonyl;
    • extraordinarily preferably hydrogen, fluorine, methyl, ethyl, trifluoromethyl, chloromethyl, 2-chloroeth-1-yl, methoxy, ethoxy, 2-methylprop-1-oxy, hydroxyl, methylcarbonyloxy, ethylthio, formyl, methylcarbonyl, methoxycarbonyl or ethoxycarbonyl;


      or
  • R4 and R5 together form a C2-C6-alkanediyl chain which can be mono- to polysubstituted by C1-C4-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C1-C4-alkyl;
    • in particular 1,4-butdiyl, 2-oxo-1,5-pentdiyl;


      or
  • R4 and R5 together with the corresponding carbon atoms form a carbonyl group
  • R6 is hydrogen, C1-C4-alkyl or C1-C4-alkoxy;
    • in particular hydrogen, methyl, methoxy or ethoxy;
  • X is O, S, CO, CR10R11;
  • Y is O, S, CR13R14;
  • R10, R11, R13, R14 are hydrogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxycarbonyl;
    • in particular hydrogen, methyl, chloromethyl or methoxycarbonyl;


      or
  • R5 and R13 together form a C2-C6-alkanediyl chain which can be mono- to polysubstituted by C1-C4-alkyl and/or which can be interrupted by oxygen or by a nitrogen which is unsubstituted or substituted by C1-C4-alkyl;
    • in particular 1,3-propdiyl;
  • R19 is hydroxyl, halogen or C1-C6-alkoxy;
    • in particular hydroxyl, chlorine, methoxy or ethoxy;


with the exception of methyl 2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoate, methyl 2-chloro-3-(4,5-dihydro-oxazol-2-yl)-4-methylsulfonylbenzoate and methyl 2,4-dichloro-3-(5-methylcarbonyloxy-4,5-dihydroisoxazol-3-yl)benzoate.


The benzoyl halides of the formula IIIα′ (where L1′=Cl, Br) can be prepared in a manner known per se by reacting the benzoic acids of the formula IIIβ with halogenating reagents such as thionyl chloride, thionyl bromide, phosgene, diphosgene, triphosgene, oxalyl chloride or oxalyl bromide.


The benzoic acids of the formula IIIβ can be prepared in a known manner from the corresponding esters of the formula IIIγ (L3=C1-C6-alkoxy) by means of acid or basic hydrolysis.




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Equally, the benzoic acids of the formula IIIβ can be obtained by reacting corresponding bromine- or iodine-substituted compounds of the formula V, with carbon monoxide and water under elevated pressure in the presence of a palladium, nickel, cobalt or rhodium transition metal catalyst and a base.




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Furthermore, it is possible to convert compounds of the formula V into the corresponding nitrites of the formula VI by a Rosenmund-von Braun reaction (cf., for example, Org. Synth. Vol III (1955), 212) and to convert these nitrites into the compounds of the formula IIIβ by subsequent hydrolysis.


The esters of the formula IIIγ can be obtained by reacting arylhalogen compounds or arylsulfonates of the formula VII, where L4 is a leaving group such as bromine, iodine, triflate, fluorosulfonyloxy and the like with heterocyclyl stannates (Stille couplings), heterocyclyl-boron compounds (Suzuki couplings) or heterocyclyl-zinc compounds (Negishi reaction) VIII, where M is Sn(C1-C4-alkyl)3, B(OH)2, ZnHal (where Hal=chlorine, bromine) and the like, respectively, in a manner known per se (cf., for example, Tetrahedron Lett. 27 (1986), 5269) in the presence of a palladium or nickel transition metal catalyst and in the presence or absence of a base.




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Equally, it is possible to obtain esters of the formula IIIγ by synthesizing the heterocycle which is bonded in the 3-position.


For example, 1,2,4-oxadiazolin-3-yl derivatives (IIIγ where X═O, Y═NH) can be prepared from amidoximes of the formula IX by condensation with aldehydes or ketones (cf., for example, Arch. Phar. 326 (1993), 383-389).




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Thioamides of the formula X are suitable precursors for 2-thiazolinyl derivatives I (where X═CR10R11, Y═S) (cf., for example, Tetrahedron 42 (1986), 1449-1460).




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2-Oxazolinyl, 2-thiazolinyl and 2-imidazolinyl derivatives (IIIγ where X═CR10R11, Y═O or Y═S or Y═NH) are accessible from the carboxylic acids of the formula XI (cf., for example, Tetrahedron Let. 22 (1981), 4471-4474).




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1,3-Thiazol-5(4H)-thion-2-yl (cf., for example, Helv. Chim. Acta 69 (1986), 374-388) and 5-oxo-2-imidazolin-2-yl derivatives (cf., for example, Heterocycles 29 (1989), 1185-1189) (III where X═CR10R11, Y═S or Y═NH) can be prepared by processes known from the literature from carboxylic acid halides of the formula XII where Hal is halogen, in particular from carboxylic acid chlorides.




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The oximes of the formula XIII can be converted into 4,5-dihydroisoxazol-3-yl derivatives (IIIγ where X═O, Y═CR13R14) in a manner known per se via the hydroxamic acid chlorides XIV as intermediates. From the latter, nitrile oxides are prepared in situ, and these nitrile oxides react with alkenes to give the desired products (cf., for example, Chem. Ber. 106 (1973), 3258-3274). 1,3-Dipolar cycloaddition reactions of chlorosulfonyl isocyanate with nitrile oxides yield 1,2,4-oxadiazolin-5-on-3-yl derivatives (IIIγ where X═O, Y═NH) (cf., for example, Heterocycles 27 (1988), 683-685).




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The aldehydes of the formula XIV can be converted into 2,4-dihydro-1,2,4-triazol-3-on-5-yl derivatives (IIIγ where X═NR9, X═NR12) via the semicarbazones as intermediates (cf., for example, J. Heterocyclic Chem. 23 (1986), 881-883).




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2-Imidazolinyl derivatives (IIIγ where X═CR10R11, Y═NH) can also be prepared from benzonitriles of the formula XV using known methods (cf., for example, J. Org. Chem. 52 (1987), 1017-1021).\




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1,3-Dipolar cycloaddition reactions of diazoalkanes or nitriloimines with arylalkenes of the formula XVI can be used for synthesizing 3-pyrazolinyl derivatives (IIIγ where X═NH, Y═CHR13)




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The bromine- or iodine-substituted compounds of the formula V which are used as starting compounds can be obtained from corresponding anilines by method similar to those known from the literature, for example by Sandmeyer reaction, and the anilines, in turn, are synthesized by reducing suitable nitro compounds. The bromine-substituted compounds of the formula V can additionally be obtained by direct bromination of suitable starting materials (cf. Monatsh. Chem. 99 (1968), 815-822).


The nitriles of the formula VI can be obtained as described above. Equally, it is possible to synthesize them from corresponding anilines by means of a Sandmeyer reaction.


The starting compounds of the formula VII are known (cf., for example, Coll. Czech. Chem. Commun. 40 (1975), 3009-3019) or can be prepared readily by a suitable combination of known syntheses.


For example, the sulfonates VII (L4=OSO2CF3, OSO2F) can be obtained from the corresponding phenols, which, in turn, are known (cf., for example, EP-A 195 247) or can be prepared by known methods (cf., for example, Synthesis 1993, 735-762).


The halogen compounds VII (L4=Cl, Br or I) can be obtained, for example, from the corresponding anilines of the formula XIX by a Sandmeyer reaction.


The amidoximes of the formula IX, the thioamides of the formula X and the carboxylic acids of the formula XI can be synthesized from the nitriles of the formula XV in a manner known per se.


Furthermore, it is possible to prepare the carboxylic acids of the formula XI from the aldehydes of the formula XIV by known processes (cf., for example, J. March, Advanced Organic Chemistry, 3rd edition (1985), p. 629 et seq., Wiley-Interscience Publication).


The carboxylic acid halides of the formula XII can be obtained from the corresponding carboxylic acids of the formula XI by methods similar to standard processes.


The oximes of the formula XIII are advantageously obtained by reacting aldehydes of the formula XIV with hydroxylamine in a manner known per se (cf., for example, J. March, Advanced Organic Chemistry, 3rd ed. (1985), pp. 805-806, Wiley-Interscience Publication).


Those aldehydes of the formula XIV which are not already known can be prepared by methods similar to known processes. Thus, they can be synthesized from methyl compounds of the formula XVII by means of bromination, for example with N-bromosuccinimide or 1,3-dibromo-5,5-dimethylhydantoin, followed by oxidation (cf. Synth. Commun. 22 (1992), 1967-1971).


The oximes of the formula XIII can also be converted into nitrites of the formula XV by processes which are-known per se (cf., for example, J. March, Advanced Organic Chemistry, 3rd ed. (1985), pp. 931-932, Wiley-Interscience Publication).


Arylalkenes of the formula XVI can be synthesized starting from the halogen compounds or sulfonates of the formula VII (L4=Br, Cl, OSO2CF3, OSO2F) by, inter alia, Heck reaction with olefins in the presence of a palladium catalyst (cf., for example, Heck, Palladium Reagents in Organic Synthesis, Academic Press, London 1985; Synthesis 1993, 735-762).




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PREPARATION EXAMPLES
4-[2-Chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl]-5-hydroxy-1-methyl-1H-pyrazole (compound 3.35)

43.60 g (0.13 mol) of 2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl chloride in 375 ml of anhydrous dioxane and 13.56 g (0.134 mol) of triethylamine in 375 ml of anhydrous dioxane are simultanouesly added dropwise at room temperature under a protective gas atmosphere to a solution 12.74 g (0.13 mol) of 5-hydroxy-1-methylpyrazole and 300 ml of anhydrous dioxane. After the reaction mixture had been stirred for 2 hours at room temperature, it was filtered through silica gel and the residue was washed with dioxane. The eluate was concentrated in vacuo to approximately 500 ml, and 17.94 by(0.13 mol) of dried, finely powdered potassium carbonate were added. After the mixture had been refluxed for 6 hours, the solvent was distilled off in vacuo and the residue was taken up in approximately 700 ml of water. Insoluble constituents were filtered off, and the pH of the filtrate was brought to 2-3 by slow addition of 10% strength hydrochloric acid. The precipitate which formed was filtered off with suction. This gave 46.16 g (92% of theory) of 4-[2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl]-5-hydroxy-1-methyl-1H-pyrazole.


(m.p.>250° C.)


Table 3 shows the above compound and, in addition, other 3-heterocyclyl-substituted benzoyl derivatives of the formula I which were prepared, or can be prepared, in a similar manner (if the end products had not precipitated upon acidification with 10% strength hydrochloric acid, they were extracted with ethyl acetate or dichloromethane; the organic phase was subsequently dried and concentrated in vacuo):










TABLE 3








I




embedded image


































Physical













data













m.p.













[° C.];














1H NMR [δ


No.
R1
R2
R3
X
R4
R5
Y
R16
Z
R18
in ppm]





3.1
Cl
Cl
H
O
H
H
CH2
n-C4H9
H
H
116-117


3.2
Cl
Cl
H
O
H
H
CH2
i-C4H9
H
H
148-151


3.3
Cl
Cl
H
O
H
H
CH2
n-C4H9
C2H5SO2
H
0.95(t); 1.32(m);













1.62(t);













1.92(quin);













3.30(t);













3.78(quar)













4.17(t); 4.61(t);













7.42(d); 7.48(m).


3.4
Cl
Cl
H
O
H
H
CH2
i-C4H9
i-C4H9SO2
H
0.96(d); 1.21(d);













2.33(m); 2.48(m);













3.30(t); 3.67(d);













3.97(d); 4.58(t);













7.42(d); 7.50(m).


3.5
Cl
Cl
H
O
H
H
CH2
n-C3H7
i-C4H9SO2
H
0.97(t); 1.20(d);













1.96(m); 2.49(m);













3.30(t); 3.68(d);













4.12(t); 4.59(t);













7.42(d); 7.49(d);













7.52(s).


3.6
Cl
Cl
H
O
H
H
CH2
n-C3H7
C2H5SO2
H
0.97(t),1.12(d);













1.63(t); 1.94(m);













3.29(t); 3.76(q);













4.14(t); 4.60(t);













7.42(d),7.48(d);













7.51(s).


3.7
Cl
SO2CH3
H
O
COOC2H5
H
CH2
CH3
H
H
70-75


3.8
Cl
SO2CH3
H
O
COOC2H5
H
CH2
C2H5
H
H
65-70


3.9
Cl
SO2CH3
H
O
CH3
H
CH2
CH3
H
H
230-235


3.10
Cl
SO2CH3
H
O
CH3
H
CH2
C2H5
H
H
210-215


3.11
Cl
SO2CH3
H
O
CH3
H
CH2
n-C3H7
H
H
 95-100


3.12
Cl
SO2CH3
H
O
CH3
H
CH2
CH3
C2H5SO2
H
70-75


3.13
Cl
SO2CH3
H
O
CH3
H
CH2
C2H5
C2H5SO2
H
78-83


3.14
Cl
SO2CH3
H
O
CH3
H
CH2
C2H5
i-C4H9SO2
H
1.24(2d); 1.53(t);













2.52(m);













3.05(dd);













3.29(s); 3.52(dd);













3.73(d); 4.24(q),













5.05(m); 7.49(s);













7.66(d); 8.18(d).


3.15
Cl
SO2CH3
H
O
CH3
H
CH2
n-C3H7
C2H5SO2
H
0.96(t); 1.53(d);













1.68(t);













1.95(sext);













3.07(dd); 3.32(s);













3.58(dd);













3.86(quart);













4.15(t); 5.03(m);













7.46(d); 7.64(d);













8.18(d).


3.16
Cl
SO2CH3
H
O
CH3
CH3
CH2
CH3
H
H
220-225


3.17
Cl
SO2CH3
H
O
CH3
CH3
CH2
C2H5
H
H
82-86


3.18
Cl
SO2CH3
H
O
CH3
CH3
CH2
n-C3H7
H
H
70-75


3.19
Cl
SO2CH3
H
O
CH3
CH3
CH2
n-C4H9
H
H
68-73


3.20
Cl
SO2CH3
H
O
CH3
CH3
CH2
i-C4H9
H
H
45-50


3.21
Cl
SO2CH3
H
O
C2H5
H
CH2
CH3
H
H
220-225


3.22
Cl
SO2CH3
H
O
C2H5
H
CH2
C2H5
H
H
170-175


3.23
Cl
SO2CH3
H
O
H
H
CH2
n-C3H7
H
H
65-70


3.24
Cl
SO2CH3
H
O
H
H
CH2
n-C4H9
H
H
55-60


3.25
Cl
SO2CH3
H
O
H
H
CH2
i-C4H9
H
H
58-63


3.26
Cl
SO2CH3
H
O
H
H
CH2
n-C4H9
C2H5SO2
H
78-83


3.27
Cl
SO2CH3
H
O
H
H
CH2
n-C4H9
i-C4H9SO2
H
0.94(t); 1.19(d);













1.22(t); 1.38(m);













1.74(br); 1.91(m);













2.53(m); 3.26(s);













4.45(t); 3.76(d);













4.18(t); 4.62(t);













7.45(s); 7.64(d);













8.16(d).


3.28
Cl
SO2CH3
H
O
H
H
CH2
i-C4H9
i-C4H9SO2
H
0.96(d); 1.21(d);













2.33(m); 2.51(m);













3.75(d); 3.99(d);













4.61(t); 7.45(s);













7.66(d); 8.17(d).


3.29
Cl
SO2CH3
H
O
H
H
CH2
i-C4H9
C2H5SO2
H
0.97(d); 1.66(t);













2.36(m); 3.29(s);













3.43(t); 3.82(q);













3.99(d); 4.60(t);













7.47(s); 7.68(d);













8.18(d).


3.30
Cl
SO2CH3
H
O
H
H
CH2
CH3
C2H5SO2
H
1.68(t); 3.29(s);













3.43(t); 3.78(q);













3.92(s); 3.63(t);













7.46(s); 7.62(d);













8.17(d).


3.31
Cl
SO2CH3
H
O
H
H
CH2
CH3
i-C4H9SO2
H
1.23(d); 2.53(m),













3.28(s); 3.43(t);













3.70(d); 3.91(s);













4.61(t); 7.48(s);













7.66(d); 8.18(d).


3.32
Cl
Cl
H
O
H
H
CH2
n-C3H7
H
H
119-121


3.33
Cl
Cl
H
O
H
H
CH2
CH3
H
CH3
115-117


3.34
Cl
NO2
H
O
H
H
CH2
C2H5
H
H
217-218


3.35
Cl
SO2CH3
H
O
H
H
CH2
CH3
H
H
>250


3.36
Cl
Cl
H
O
H
H
CH2
C2H5
H
H
125-128


3.37
Cl
SO2CH3
H
O
H
H
CH2
C2H5
n-C3H7SO2
H
78-83


3.38
Cl
SO2CH3
H
O
H
H
CH2
C2H5
C2H5SO2
H
1.52(t); 1.68(t);













3.29(s); 3.43(t);













3.82(q); 4.24(q);













4.63(t); 7.48(s);













7.65(d); 8.07(d).


3.39
Cl
SO2C2H5
H
O
CH3
CH3
CH2
CH3
H
H
>200


3.40
Cl
SO2C2H5
H
O
CH3
H
CH2
CH3
H
H
220-223


3.41
Cl
SO2C2H5
H
O
CH3
H
CH2
C2H5
H
H
>230


3.42
Cl
SO2-n-C3H7
H
O
CH3
H
CH2
CH3
H
H
1.12(t); 1.53(d);













1.76(quin);













3.18(dd); 3.38(t);













3.55(dd); 3.73(s);













5.04(m);













5.55(s, br.);













7.37(s); 7.68(d);













8.13(d).


3.43
Cl
SO2-n-C3H7
H
O
CH3
H
CH2
C2H5
H
H
1.07(t); 1.50(m);













1.78(quin)













3.07(dd); 3.39(t);













3.55(dd); 4.12(t);













5.08(m); 7.38(s);













7.69(d); 8.11(d).


3.44
Cl
SO2CH3
H
CH2
H
H
O
CH3
H
H


3.45a)
Cl
SO2CH3
H
C(CH3)2
H
H
O
CH3
H
H
1.33(s); 3.40(s);













4.17(s); 7.43(s);













7.79(d); 8.04(d).


3.46
Cl
SO2CH3
H
O
H
H
CH2
C2H5
Na+
H
218-220


3.47
Cl
SO2CH3
H
O
H
H
CH2
C2H5
K+
H
193


3.48
Cl
SO2CH3
H
O
H
H
CH2
C2H5
Li+
H
>230


3.49
Cl
SO2CH3
H
O
H
H
CH2
C2H5
NH4+
H
170-175


3.50
Cl
SO2CH3
H
O
H
H
CH2
CH3
Na+
H
>240


3.51
Cl
SO2CH3
H
O
H
H
CH2
CH3
K+
H
206-214


3.52
Cl
SO2CH3
H
O
H
H
CH2
CH3
Li+
H
>240


3.53
Cl
SO2CH3
H
O
H
H
CH2
CH3
NH4+
H


3.54a)
Cl
SO2CH3
H
C(CH3)2
H
H
O
C2H5
H
H
1.27(t); 1.36(s);













3.41(q); 4.01(q);













4.18(s); 7.47(s);













7.83(d); 8.07(d).

















3.55
Cl
SO2CH3
H
O
H
—(CH2)3CH—
C2H5
H
H
 99-104


3.56
Cl
SO2CH3
H
O
H
—(CH2)3CH—
CH3
H
H
 95-100

















3.57
Cl
SO2CH3
H
O
—(CH2)4—
CH2
CH3
H
H
230-235


3.58
Cl
SO2CH3
H
O
—(CH2)4—
CH2
C2H5
H
H
190-195


3.59
Cl
SO2CH3
H
O
—(CH2)2O(CH2)2—
CH2
C2H5
H
H
 95-100


















3.60
Cl
SO2C2H5
H
O
CH3
CH3
CH2
CH3
H
H
<230


3.61
Cl
SO2C2H5
H
O
CH3
CH3
CH2
C2H5
H
H
198-200


3.62
Cl
SO2C2H5
H
O
H
H
CH2
CH3
H
H
215-218


3.63
Cl
SO2C2H5
H
O
H
H
CH2
C2H5
H
H
213-215


3.64
Cl
SO2-n-C3H7
H
O
H
H
CH2
CH3
H
H
186-190


3.65
Cl
SO2-n-C3H7
H
O
H
H
CH2
C2H5
H
H
84-86

















3.66
Cl
SO2CH3
H
O
—(CH2)2O(CH2)2—
CH2
CH3
H
H
90-95


















3.67
Cl
SO2CH3
H
O
C2H5
C2H5
CH2
CH3
H
H
70-75


3.68
Cl
SO2CH3
H
O
C2H5
C2H5
CH2
C2H5
H
H
50-55


3.69
Cl
SO2CH3
H
O
OCH3
H
CH2
CH3
H
H
3.18-3.99(11H);













5.78(1H);













7.50(1H);













7.81(1H);













8.09(1H).


3.70
Cl
SO2CH3
H
O
CH3
H
CHCH2Cl
CH3
H
H
1.52(3H); 3.30-













4.12(8H);













4.36(1H);













4.93(1H);













7.49(1H);













7.81(1H);













8.09(1H).


3.71
Cl
SO2CH3
H
O
CH3
H
CHCH2Cl
C2H5
H
H
1.27(3H);













1.55(3H);













3.28-4.02(7H)













4.37(1H);













4.92(1H);













7.48(1H);













7.80(1H);













8.07(1H)


3.72
Cl
SO2CH3
H
C(CH3)2
H
H
O
CH3
H
H
132-135


3.73
Cl
SO2CH3
H
O
C2H5
H
CH2
CH3
H
H
 95-100


3.74
Cl
SO2CH3
H
O
C2H5
H
CH2
C2H5
H
H
1.16(3H);













1.27(3H);













3.20-4.00(9H);













5.89(1H);













7.50(1H);













7.82(1H);













8.07(1H).


3.75
Cl
SO2CH3
H
O
C2H5
C2H5
CH2
C2H5
K+
H
200-205


3.76
Cl
SO2C2H5
H
C(CH3)2
H
H
O
CH3
H
H
120-123


3.77
Cl
SO2-n-C3H7
H
O
CH3
CH3
CH2
C2H5
H
H
152-158


3.78
Cl
SO2-n-C3H7
H
O
CH3
CH3
CH2
CH3
H
H
172-176


3.79
Cl
SO2-n-C3H7
H
O
CH3
H
CH2
CH3
H
H
188-205


3.80
Cl
SCH3
H
O
H
H
CH2
C2H5
H
H
1.29(t); 2.56(s);













3.28(t); 3.93(q);













4.49(t); 7.40(s);













7.43(d); 7.55(d).


3.81
Cl
SO2CH3
H
O
CH2Cl
H
CH2
C2H5
H
H
78-82


3.82
CH3
H
H
CH2
H
H
S
C2H5
H
H
1.44(t); 2.50(s);













3.49(t); 4.09(q);













4.53(t); 7.35(m);













7.48(d); 7.62(d).


3.83
Cl
SO2CH3
H
O
CH2Cl
H
CH2
CH3
H
H
81-85


3.84
Cl
SCH3
H
O
H
H
CH2
CH3
H
H
151-153


3.85
Cl
SOCH3
H
O
H
H
CH2
C2H5
H
H
1.28(t); 2.82(s);













3.40(m); 3.92(m);













4.52(t); 7.45(s);













7.82(d); 8.10(d).


3.86
CH3
SO2CH3
H
O
H
H
CH2
CH3
H
H
205-210


3.87
Cl
Cl
H
CH2
H
H
S
C2H5
H
H
173-179


3.88
Cl
SCH3
H
CH2
H
H
S
C2H5
H
H
1.43(t); 2.51(s);













3.59(t); 4.08(q);













4.51(t); 7.22(d);













7.41(s); 7.50(d).


3.89
Cl
SO2CH3
H
CH2
H
H
S
C2H5
H
H
1.50(t); 3.28(s);













3.62(t); 4.10(q);













4.49(t); 7.36(s);













7.68(d); 8.19(d).


3.90
CH3
SO2CH3
H
O
H
H
CH2
C2H5
H
H
174-180


3.91
Cl
SO2CH3
H
O
CH2Cl
H
CH2
CH3
H
H
77-83


3.92
Cl
SO2CH3
H
O
F
H
CH2
CH3
H
H


3.93
Cl
SO2CH3
H
O
F
H
CH2
C2H5
H
H


3.94
Cl
SO2CH3
H
O
F
F
CH2
CH3
H
H


3.95
Cl
SO2CH3
H
O
F
F
CH2
C2H5
H
H


3.96
Cl
SO2CH3
H
O
CH3
H
CHCH3
C2H5
H
H
183-184


3.97
Cl
SO2CH3
H
O
CF3
H
CH2
CH3
H
H
223-225


3.98
Cl
SO2CH3
H
O
CF3
H
CH2
C2H5
H
H
183-184


3.99
Cl
SO2CH3
H
O
SC2H5
H
CH2
CH3
H
H
195-196


3.100
Cl
SO2CH3
H
O
SC2H5
H
CH2
C2H5
H
H
199-200


3.101
Cl
SO2CH3
H
O
CH3
H
CHCH3
CH3
H
H
230-233


3.102
Cl
SO2CH3
H
O
CHCl(CH3)
H
CH2
C2H5
H
H
102-107


3.103
Cl
SO2CH3
H
O
CHCl(CH3)
H
CH2
CH3
H
H
80-85


3.104
Cl
SO2CH3
H
O
n-C3H7
H
CH2
CH3
H
H


3.105
Cl
SO2CH3
H
O
n-C3H7
H
CH2
C2H5
H
H


3.106
Cl
SO2CH3
H
O
H
H
CH2
CH3

+NH2(CH3)2
H
200


3.107
Cl
SO2CH3
H
O
H
H
CH2
CH3

+NH2(CH2CH2OH)
H
187


3.108
Cl
SO2CH3
H
O
H
H
CH2
CH3

+NH3(CH2CH2OCH2
H
180











CH2OH)


3.109
SCH3
SCH3
H
O
H
H
CH2
CH3
H
H
2.33(s); 2.51(s);













3.40(t); 3.70(s);













4.58(t); 5.15(brs);













7.21(s); 7.31(d);













7.42(d)


3.110
SCH3
SCH3
H
O
H
H
CH2
C2H5
H
H
1.38(t); 2.33(s);













2.49(s); 3.41(t);













4.10(q); 4.58(t);













7.25(s); 7.32(d);













7.41(d);













7.82(brs).


3.111
SO2CH3
SO2CH3
H
O
H
H
CH2
CH3
H
H
oil


3.112
SO2CH3
SO2CH3
H
O
H
H
CH2
C2H5
H
H
oil






a)Prepared from 2-chloro-3-(1′-chloro-2′,2′-dimethylethylaminocarbonyl)-4-methylsulfonylbenzoyl chloride with two equivalents of potassium carbonate.






The syntheses of some starting materials are given below:


2-Chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoyl chloride (compound 4.5)

Step a) 2-Chloro-3-methyl-4-methylthioacetophenone






    • A solution of 157 g (2 mol) of acetyl chloride in 420 mol of 1,2-dichlorethane was added dropwise to a suspension of 286 g (2.14 mol) of aluminum trichloride in 420 ml of 1,2-dichloroethane at 15-20° C. A solution of 346 g (2 mol) of 2-chloro-6-methylthiotoluene in 1 l of 1,2-dichlorethane was subsequently added dropwise. After the reaction mixture had been stirred for 12 hours, it was poured into a mixture of 3 l of ice and 1 l of concentrated HCl. The mixture was extracted with methylene chloride, and the organic phase was washed with water, dried with sodium sulfate and concentrated. The residue was distilled in vacuo. This gave 256 g (60% of theory) of 2-chloro-3-methyl-4-methylthioacetophenone.





(m.p.: 46° C.)


Step b) 2-Chloro-3-methyl-4-methylsulfonylacetophenone






    • 163.0 g (0.76 mol) of 2-chloro-3-methyl-4-methylthioacetophenone were dissolved in 1.5 l of glacial acetic acid, 18.6 g of sodium tungstate were added, and 173.3 g of a 30% strength hydrogen peroxide solution were added dropwise with cooling. Stirring was continued for 2 days and the mixture was subsequently diluted with water. The solid which had precipitated was filtered off with suction, washed with water and dried. This gave 164.0 g (88% of theory) of 2-chloro-3-methyl-4-methylsulfonyl-acetophenone.





(m.p.: 110-111° C.)


Step c) 2-Chloro-3-methyl-4-methylsulfonylbenzoic acid






    • 82 g (0.33 mol) of 2-chloro-3-methyl-4-methyl-sulfonylacetophenone were dissolved in 700 ml of dioxane, and 1 l of a 12.5% strength sodium hypochlorite solution was added at room temperature. Stirring was continued for 1 hour at 80° C. After cooling, two phases formed, of which the bottom phase was diluted with water and acidifed weakly. The solid which had precipitated was filtered off with suction, washed with water and dried. This gave 60 g (73% of theory) of 2-chloro-3-methyl-4-methylsulfonylbenzoic acid.





(m.p.: 230-231° C.)


Step d) Methyl 2-chloro-3-methyl-4-methylsulfonylbenzoate






    • 100 g (0.4 mol) of 2-chloro-3-methyl-4-methyl-sulfonylbenzoic acid were dissolved in 1 l of methanol and hydrogen chloride gas was passed in for 5 hours at reflux temperature. The mixture was subsequently concentrated. This gave 88.5 g (84% of theory) of methyl 2-chloro-3-methyl-4-methylsulfonylbenzoate.





(m.p.: 107-108° C.)


Step e) Methyl 3-bromomethyl-2-chloro-4-methylsulfonylbenzoate






    • 82 g (0.1 mol) of methyl 2-chloro-3-methyl-4-methyl-sulfonylbenzoate are dissolved in 2 l of tetrachloromethane, and 56 g (0.31 mol) of N-bromosuccinimide are added in portions with exposure to light. The reaction mixture was filtered, the filtrate was concentrated, and the residue was taken up in 200 ml of methyl tert-butyl ether. The solution was treated with petroleum ether and the solid which had precipitated was filtered off with suction and dried. This gave 74.5 g (70% of theory) of methyl 3-bromomethyl-2-chloro-4-methylsulfonylbenzoate.





(m.p.: 74-75° C.)


Step f) Methyl 2-chloro-3-formyl-4-methylsulfonylbenzoate






    • A solution of 41.0 g (0.12 mol) of methyl 3-bromomethyl-2-chloro-4-methylsulfonylbenzoate in 250 ml of acetonitrile was treated with 42.1 g (0.36 mol) of N-methylmorphline N-oxide. The batch was stirred for 12 hours at room temperature and subsequently concentrated, and the residue was taken up in ethyl acetate. The solution was extracted with water, dried with sodium sulfate and concentrated. This gave 31.2 g (94% of theory) of methyl 2-chloro-3-formyl-4-methylsulfonylbenzoate





(m.p.: 98-105° C.)


Step g) 2-Chloro-3-hydroxyiminomethyl-4-methylsulfonylbenzoic acid






    • 15.00 g (54 mmol) of methyl 2-chloro-3-formyl-4-methyl-sulfonylbenzoate and 4,20 g (60 mmol) of hydroxylamine hydrochloride were taken up in 300 ml of methanol, and a solution of 3.18 g (30 mmol) of sodium carbonate in 80 ml of water was added dropwise. After the mixture had been stirred for 12 hours at room temperature, the methanol was distilled off, the residue was diluted with water and the mixture was extracted with diethyl ether. After the organic phase had been dried, the solvent was removed. This gave 14.40 g (91% of theory) of methyl 2-chloro-3-hydroxyiminomethyl-4-methylsulfonylbenzoate.





(m.p.: 126-128° C.).


Step h) Methyl 2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoate (compound 4.3)






    • Ethylene was passed for 30 minutes at 15-20° C. into a solution of 158.0 g (0.54 mol) of methyl 2-chloro-3-hydroxyiminomethyl-4-methylsulfonylbenzoate and 1 l of dichloromethane. After 1.6 g of sodium acetate had been added, 454 ml of sodium hydrochlorite solution were added dropwise at 10° C. while simultaneously passing in ethylene. Ethylene was subsequently passed in at 10° C. for a further 15 minutes. After the mixture had been stirred for 12 hours, the phases were separated, and the organic phase was washed with water, dried and concentrated. This gave 156.5 g (90% of theory) of methyl 2-chloro-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoate.





(1H NMR (δ in ppm): 3.24 (s); 3.42 (t); 3.99 (s); 4.60 (t); 7.96 (d); 8.10 (d)).


Step i) 2-Chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoic acid (compound 4.4)






    • A solution of 32.8 g of sodium hydroxide, dissolved in 330 ml of methanol, was slowly added dropwise to a mixture of 170.0 g (0.54 mol) of methyl 2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoate and 1 l of methanol at 40-45° C. The suspension was stirred for 5 hours at 50° C. After the solvent had been distilled off, the residue was taken up in 1.5 l of water, and the aqueous phase was extracted three times with ethyl acetate. The aqueous phase was acidified with hydrochloric acid and extracted three times with ethyl acetate. The combined organic phases were subsequently washed to neutrality with water, dried and concentrated. This gave 148.8 g (91% of theory) of 2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoic acid.





(1H NMR (δ in ppm): 3.26 (s); 3.45 (t); 4.63 (t); 8.15 (s) 8.53 (s, br)).


Step j) 2-Chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl chloride (compound 4.5)






    • 74.8 g (0.63 mol) of thionyl chloride in 50 ml of dry toluene were added dropwise at 50° C. to a solution of 139.0 g of 2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoic acid, 1 ml of dimethylformamide and 1 l of dry toluene. After the mixture had been heated for 6 hours at 110° C., the solvent was distilled off. This gave 2-chloro-3-(4,5-dihydroisoxazol-3-yl)-4-methyl-sulfonylbenzoyl chloride in quantitative yield.





(1H NMR (δ in ppm): 3.25 (s); 3.46 (t); 4.62 (t); 8.21 (dd)).


2-Chloro-3-(5-methyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-benzoyl chloride (compound 4.39)

Step a) Methyl 2-chloro-3-(5-methyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoate (compound 4.25)






    • Propene was passed for 30 minutes at room temperature into a solution of 15.0 g (52 mmol) of methyl 2-chloro-3-hydroxyiminomethyl-4-methylsulfonylbenzoate and 200 ml of dichloromethane. After 1.6 g of sodium acetate had been added, 42.8 ml of sodium hydrochlorite [sic] solution were added dropwise at room temperature while simultaneously passing in propene. Propene was subsequently passed in for a further 15 minutes at room temperature. After the mixture had been refluxed for 3 hours, it was stirred for 12 hours at room temperature, propene was again passed in for 5 hours under reflux, and the mixture was stirred for a further 12 hours at room temperature. After the phases had been separated, the organic phase was washed with water, dried and concentrated. This gave 15.5 g (89% of theory) of methyl 2-chloro-(5-methyl-4,5-dihydroisoxazol-3-yl)-4-methyl-sulfonylbenzoate.





(m.p.: 130-135° C.)


Step b) 2-Chloro-3-(5-methyl-4,5-dihydroisoxazol-3-yl)-4-methyl-sulfonylbenzoic acid (compound 4.26)






    • A solution of 3.52 g (88 mmol) of sodium hydroxide, dissolved in 100 ml of methanol, was slowly added dropwise to a mixture of 15.00 g (45 mmol) of methyl 2-chloro-3-(5-methyl-4,5-dihydroisoxazol-3-yl)-4-methyl-sulfonylbenzoate and 200 ml of methanol. The suspension was stirred for 48 hours at room temperature. After the solvent had been distilled off, the residue was taken up in water, and the aqueous phase was washed three times with ethyl acetate. The aqueous phase was acidified with hydrochloric acid and extracted three times with ethyl acetate. The combined organic phases were subsequently washed to neutrality with water, dried and concentrated. This gave 13.20 g (92% of theory) of 2-chloro-3-(5-methyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoic acid.





(m.p.: 173-178° C.)


Step c) 2-Chloro-3-(5-methyl-4,5-dihydroisoxazol-3-yl)-4-methyl-sulfonylbenzoyl chloride (compound 4.39)






    • 5.7 g (51 mmol) of thionyl chloride were added dropwise at room temperature to a solution of 13.0 g (41 mmol) of 2-chloro-3-(5-methyl-4,5-dihydroisoxazol-3-yl)-4-methyl-sulfonylbenzoic acid, 1 ml of dimethylformamide and 250 ml of dry toluene. The mixture was subsequently refluxed until the reaction was complete. After cooling, the solvent was distilled off. This gave 14.2 g of 2-chloro-3-(5-methyl-4,5-dihydroisoxazol-3-yl)-4-methyl-benzoyl chloride in quantitative yield.





2-Chloro-3-(1′-chloro-2′,2′-dimethylethylaminocarbonyl)-4-methyl-sulfonylbenzoyl chloride

Step a) Methyl 2-chloro-3-hydroxycarbonyl-4-methyl-sulfonylbenzoate






    • 13.8 g (0.11 mol) of sodium hydrogen phosphate monohydrate in 170 ml of water, 49.3 g (0.43 mol) of 30% strength hydrogen peroxide solution and 66.2 g (0.59 mol) of 80% strength aqueous sodium chlorite solution were added in succession at 5° C. to a solution of 115.3 g (0.42 mol) of methyl 2-chloro-3-formyl-4-methyl-sulfonylbenzoate and [sic] 2000 ml of acetonitrile. The reaction solution was subsequently stirred for 1 hour at 5° C. and for 12 hours at room temperature. The pH was then brought to 1 with 10% strength hydrochloric acid, and 1500 ml of aqueous 40% strength sodium hydrogen sulfite solution were added. After the mixture had been stirred for 1 hour at room temperature, the aqueous phase was extracted three times with ethyl acetate. The combined organic phases were washed with sodium hydrogen sulfite solution and dried. After the solvent had been distilled off, 102.0 g of methyl 2-chloro-3-hydroxycarbonyl-4-methylsulfonylbenzoate were obtained.





(1H NMR (δ in ppm): 3.34 (s); 3.93 (s); 8.08 (s); 14.50 (s, br.).)


Step b) Methyl 2-chloro-3-chlorocarbonyl-4-methylsulfonylbenzoate






    • 2 drops of dimethylformamide and 11.9 g (0.1 mol) of thionyl chloride were added to a solution of 6.0 g (0.021 mol) of methyl 2-chloro-3-hydroxycarbonyl-4-methylsulfonylbenzoate and 50 ml of dry toluene. The solution was refluxed for 4 hours. After the solvent had been removed in vacuo, 6.2 g of methyl 2-chloro-3-chlorocarbonyl-4-methylsulfonylbenzoate were obtained.





(1H NMR (δ in ppm): 3.21 (s); 4.02 (s); 8.02 (d); 8.07 (d).)


Step c) Methyl 2-chloro-3-(1′-hydroxy-2′,2′-dimethylethylaminocarbonyl)-4-methylsulfonylbenzoate






    • A solution of 7.80 g (25 mmol) of methyl 2-chloro-3-chlorocarbonyl-4-methylsulfonylbenzoate was added dropwise at 0-5° C. to a solution of 4.54 g (50 mmol) of 2,2-dimethylethanolamine in 40 ml of dichloromethane. After the reaction solution had been stirred for 6 hours at room temperature, it was extracted three times with water, dried and concentrated. This gave 8.20 g (80% of theory) of methyl 2-chloro-3-(1′-hydroxy-2′,2′-dimethylethylaminocarbonyl)-4-methylsulfonylbenzoate.





(m.p.: 70-72° C.).


Step d) Methyl 2-chloro-3-(1′-chloro-2′,2′-dimethyl-ethylaminocarbonyl)-4-methylsulfonylbenzoate






    • A mixture of 6.9 g (20 mmol) of methyl 2-chloro-3-(1′-hydroxy-2′,2′-dimethylethylamino-carbonyl)-4-methylsulfonylbenzoate and 5 ml of thionyl chloride was stirred for 6 hours at room temperature. The solution was diluted with 50 ml of dichloromethane and subsequently concentrated. The residue was dissolved in 20 ml of dichloromethane. The addition of cyclohexane resulted in a crystalline precipitate which was filtered off with suction and dried. This gave 6.4 g (88% of theory) of methyl 2-chloro-3-(1′-chloro-2′,2′-dimethylethylaminocarbonyl)-4-methylsulfonylbenzoate.


      Step e) 2-Chloro-3-(4′,4′-dimethyl-4′,5′-dihydroxazol-2-yl)-4-methylsulfonylbenzoic acid (compound 4.38)

    • A solution of 5.82 g (15 mmol) of methyl 2-chloro-3-(1′-chloro-2′,2′-dimethylethyl-aminocarbonyl)-4-methylsulfonylbenzoate and 0.81 g (20 mmol) of sodium hydroxide in 80 ml of methanol was stirred for 8 hours at room temperature. After the solvent had been distilled off, the residue was taken up in water and the mixture was washed three times with ethyl acetate. The aqueous phase was acidified with hydrochloric acid and extracted three times with ethyl acetate. After the organic phase had been dried, the solvent was removed in vacuo. This gave 3.10 g (56% of theory) of 2-chloro-3-(4′,4′-dimethyl-4′,5′-dihydrooxazol-2-yl)-4-methylsulfonylbenzoic acid.





(1H NMR (δ in ppm): 1.34 (s); 3.40 (s); 4.13 (s); 8.07 (s); 13.95 (s, br)).


Step f) 2-Chloro-3-(1′-chloro-2′,2′-dimethylethylaminocarbonyl)-4-methylsulfonylbenzoyl chloride






    • A solution of 3.00 g (9 mmol) of 2-chloro-3-(4′,4′-dimethyl-4′,5′-dihydrooxazol-2-yl)-4-methylsulfonyl-benzoic acid, 1.43 g of thionyl chloride and 1 drop of dimethylformamide in 80 ml of dry toluene was refluxed for 3 hours. After cooling, the solvent was distilled off in vacuo. This gave 3.43 g (86% of theory) of 2-chloro-3-(1′-chloro-2′,2′-dimethylethylaminocarbonyl)-4-methylsulfonylbenzoyl chloride.





Methyl 2-chloro-3-(1,3,4-oxathiazolin-2-on-5-yl)-4-methylsulfonylbenzoate (compound 4.22)

Step a) Methyl 3-aminocarbonyl-2-chloro-4-methylsulfonylbenzoate






    • Ammonia was passed for 2 hours into a solution of 15.0 g (48 mmol) of methyl 2-chloro-3-chlorocarbonyl-4-methylsulfonylbenzoate and 300 ml of dry dioxane. The precipitate formed was filtered off with suction and the filtrate was concentrated. This gave 15.2 g of methyl 3-aminocarbonyl-2-chloro-4-methylsulfonylbenzoate in quantitative yield.


      Step b) Methyl 2-chloro-3-(1,3,4-oxathiazolin-2-on-5-yl)-4-methylsulfonylbenzoate

    • 9.80 g (75 mmol) of chlorocarbonylsulfenyl chloride were added dropwise to a solution of 4.37 g (15 mmol) of methyl 3-aminocarbonyl-2-chloro-4-methylsulfonylbenzoate in 150 ml of dry toluene. After the mixture had been stirred for 48 hours under reflux, the solvent is removed in vacuo and the residue is chromatographed on silica gel (eluent:ethyl acetate/cyclohexane=1/1). This gave 3.70 g (70% of theory) of methyl 2-chloro-3-(1,3,4-oxathiazolin-2-on-5-yl)-4-methylsulfonylbenzoate.





Methyl 2-chloro-4-methylsulfonyl-3-(4,5-dihydrooxazol-3-yl)-benzoate (compound 4.41)

At room temperature, 41.8 g (0.41 mol) of triethylamine and then 31.1 g (0.10 mol) of methyl 2-chloro-3-chlorocarbonyl-4-methylsulfonylbenzoate in 150 ml of toluene were added dropwise to 26.6 g (0.13 mol) of 1-amino-2-bromoethane hydrobromide in 500 ml of toluene. The mixture was heated under reflux for 5 hours and then stirred at room temperature for 12 hours, another 5.0 g (0.02 mol) of 1-amino-2-bromoethane hydrobromide were added and the mixture was heated under reflux for 7.5 hours. The reaction mixture was allowed to cool, diluted with ethyl acetate, washed with water, dried and concentrated. The residue was then recrystallized from methyl tert-butyl ether/ethyl acetate. 14.5 g (46% of theory) of methyl 2-chloro-4-methyl-sulfonyl-3-(4,5-dihydrooxazol-2-yl)benzoate were obtained.


2-Chloro-3-(5-methoxy-5-methyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoic acid (compound 4.60)

Step a) Methyl 2-chloro-3-(5-methoxy-5-methyl-4,5-dihydro-isoxazol-3-yl)-4-methylsulfonylbenzoate






    • 7.3 g (102 mmol) of 2-methoxy-1-propene, 28 ml of sodium hypochlorite solution (12.5% strength) and a spatula-tip of sodium acetate were added successively to 10.0 g (34 mmol) of methyl 2-chloro-3-(hydroxyiminomethyl)-4-methylsulfonylbenzoate in 200 ml of methylene chloride. The mixture was stirred at room temperature for 12 hours, the solvent was removed and the residue was taken up in ethyl acetate, washed with water, dried and concentrated. The residue was chromatographed over silica gel (eluent: cyclohexane:ethyl acetate=3:2). This gave 5.8 g (47% of theory) of methyl 2-chloro-3-(5-methoxy-5-methyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoate.





(mp.: 100-105° C.)


Step b) 2-Chloro-3-(5-methoxy-5-methyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoate






    • At reflux temperature, 5.5 g (15.0 mmol) of methyl 2-chloro-3-(5-methoxy-5-methyl-4,5-dihydroisoxazol-3-yl)-4-methylsulfonylbenzoate in 100 ml of pyridine were added dropwise to 5.0 g (37.5 mmol) of lithium iodide in 200 ml of pyridine. The mixture was stirred at this temperature for 4 hours and then cooled, the solvent was distilled off and the residue was taken up in toluene and reconcentrated. The residue was subsequently admixed with water and washed with methylene chloride, and the pH was adjusted to 1 using hydrochloric acid. The aqueous phase was extracted with methylene chloride and the resulting organic phase was dried and concentrated. This gave 4.7 g (90% of theory) of 2-chloro-(5-methoxy-5-methyl-4,5-di-hydroisoxazol-3-yl)-4-methylsulfonylbenzoate.





(mp.: 40-45° C.)


Methyl 2-chloro-3-(2-methyl-2H-1,3,4-dioxazol-5-yl)-4-methyl-sulfonylbenzoate (compound 4.44)

8.0 g (27.4 mmol) of methyl 2-chloro-3-(hydroxyiminomethyl)-4-methylsulfonylbenzoate in 150 ml of methylene chloride were admixed dropwise with 16.0 g (27.4 mmol) of a 12.5% strength sodium hypochlorite solution, and a spatula-tip of sodium acetate was added. After 1 hour, 34.4 g (0.74 mol) of acetaldehyde were added a little at a time within a period of 36 hours, and the mixture was slowly heated to 55° C. The mixture was subsequently stirred at room temperature for 48 hours, washed with water, dried and concentrated. The residue was then taken up in methylene chloride, 10.0 g (0.23 mol) of acetaldehyde and a spatula-tip of sodium acetate were added and the mixture was heated under reflux for 8 hours. After 72 hours, a further 10.0 g (0.23 mol) of acetaldehyde were added and the mixture was stirred at room temperature. The mixture was subsequently washed with water, dried and concentrated. The residue was passed through silica gel (eluent: isopropanol:cyclohexane=1:9). This gave 5.0 g (55% of theory) of methyl 2-chloro-3-(2-methyl-2H-1,3,4-dioxazol-5-yl)-4-methylsulfonylbenzoate.


Table 4 which follows lists the compounds which have been described above and also further benzoic acid derivatives of the formula III which were prepared, or can be prepared, by a similar method.










TABLE 4








III




embedded image






























Physical data











m.p. [° C.];


No.
R1
R2
R3
X
R4
R5
Y
R19

1H NMR [δ in ppm]





4.1
Cl
Cl
H
O
H
H
CH2
OCH3
3.29(t); 3.91(s); 4.58(t);











7.46(d); 7.83(d).


4.2
Cl
Cl
H
O
H
H
CH2
OH
3.28(t); 4.60(t); 7.02(s, br);











7.46(d); 7.98(d).


4.3
Cl
SO2CH3
H
O
H
H
CH2
OCH3
3.24(s); 3.42(t); 3.99(s);











4.60(t); 7.96(d); 8.10(d).


4.4
Cl
SO2CH3
H
O
H
H
CH2
OH
3.26(s); 3.45(t); 4.63(t);











8.15(s); 8.53(s, br).


4.5
Cl
SO2CH3
H
O
H
H
CH2
Cl
3.25(s); 3.46(t); 4.62(t);











8.21(dd).


4.6
Cl
Cl
H
C(CH3)2
H
H
O
OH
1.31(s); 4.16(s); 7.69(d);











7.90(d); 13.8(s, br).


4.7
Cl
SO2C2H5
H
O
CH3
CH3
CH2
OCH3
1.25(t); 1.57(s); 3.21(s);











3.42(q); 3.99(s); 7.94(d);











8.07(d).


4.8
Cl
SO2C2H5
H
O
CH3
CH3
CH2
OH
1.13(t); 1.47(s); 3.15(s);











3.43(q); 8.06(s); 13.8(s, br).


4.9
Cl
SO2C2H5
H
O
H
H
CH2
OCH3
1.28(t); 3.41(m); 4.02(s);











4.62(t); 7.95(d); 8.06(d).


4.10
Cl
SO2C2H5
H
O
H
H
CH2
OH
137-140


4.11
Cl
SO2C2H5
H
O
CH3
H
CH2
OCH3
1.26(t); 1.53(d); 3.06(dd);











3.42(q); 3.49(dd); 5.05(m);











7.95(d); 8.07(d).


4.12
Cl
SO2C2H5
H
O
CH3
H
CH2
OH
140-143


4.13
Cl
SO2CH3
H
CH2
H
H
O
OCH3
3.30(s); 3.98(s); 4.11(t);











4.55(t); 7.97(d); 8.08(d).


4.14
Cl
SO2CH3
H
CH2
H
H
O
OH
3.38(s); 4.00(t); 4.46(t);











8.08(s).


4.15
Cl
SO2CH3
H
O
H
H
CH2
OH
3.30(s); 3.35(t); 4.15(s, br);











4.50(t); 8.05(s).


4.16
Cl
SO2-n-C3H7
H
O
CH3
CH3
CH2
OCH3
0.95(t); 1.47(s); 1.58(quin);











3.12(s); 3.31(s); 3.43(t);











3.93(s); 8.09(dd).


4.17
Cl
SO2-n-C3H7
H
O
CH3
CH3
CH2
OH
0.93(t); 1.47(s); 1.58(quin);











3.15(s); 3.42(t); 8.05(s).


4.18
Cl
SO2-n-C3H7
H
O
H
H
CH2
OCH3
0.92(t); 1.55(quin); 3.39(m);











3.93(s); 4.50(t); 8.08(dd).


4.19
Cl
SO2-n-C3H7
H
O
H
H
CH2
OH
148-150


4.20
Cl
SO2-n-C3H7
H
O
CH3
H
CH2OCH3
0.93
(t); 1.49(d); 1.58(quin);











2.94(dd); 3.42(m); 3.93(s);











4.97(m); 8.10(dd).


4.21
Cl
SO2-n-C3H7
H
O
CH3
H
CH2
OH
0.94(t); 1.39(d); 1.58(quin);











2.96(dd); 3.50(m); 4.95(m);











8.05(s).















4.22
Cl
SO2CH3
H
S
═O
O
OCH3
3.24(s); 4.02(s); 8.14(dd).
















4.23
Cl
SO2CH3
H
O
COOC2H5
H
CH2
OCH3
118-121


4.24
Cl
SO2CH3
H
O
COOC2H5
H
CH2
OH


4.25
Cl
SO2CH3
H
O
CH3
H
CH2
OCH3
130-135


4.26
Cl
SO2CH3
H
O
CH3
H
CH2
OH
173-178


4.27
Cl
SO2CH3
H
O
CH3
CH3
CH2
OCH3
1.57(s); 3.18(s); 3.27(s);











4.01(s); 7.97(d); 8.12(d).


4.28
Cl
SO2CH3
H
O
CH3
CH3
CH2
OH
1.48(s); 3.15(s); 3.34(s);











8.08(dd).


4.29
Cl
SO2CH3
H
O
C2H5
H
CH2
OCH3
0.97(t); 1.72(m); 3.10(dd);











3.32(s); 3.37(dd); 4.72(m);











8.08(dd).















4.30
Cl
SO2CH3
H
O
H
—(CH2)3—CH—
OCH3
1.57(m); 1.81(m); 2.21(m);










3.20(s); 4.02(s); 4.32(t);










5.35(dd); 7.92(d); 8.18(d).


4.31
Cl
SO2CH3
H
O
H
—(CH2)3—CH—
OH
1.72(m); 2.01(m); 3.27(s);










4.24(t); 5.23(dd); 8.05(d);










8.15(d); 13.8(s, br).















4.32
Cl
SO2CH3
H
O
—(CH2)2—O—(CH2)2—
CH2
OCH3
2.00(m); 3.23(s); 3.27(s),










3.72(m); 4.00(s); 7.96(d);










8.04(d).


4.33
Cl
SO2CH3
H
O
—(CH2)2—O—(CH2)2—
OH
78-83


4.34
Cl
SO2CH3
H
O
—(CH2)4—
CH2
OCH3
1.78(m); 2.24(m); 3.27(s);










3.36(s); 3.98(s); 7.94(d);










8.12(d).


4.35
Cl
SO2CH3
H
O
—(CH2)4—
CH2
OH
1.76(m); 2.05(m); 3.30(s);










3.33(s); 8.09(dd).
















4.36
Cl
SO2CH3
H
O
C2H5
C2H5
CH2
OCH3
1.00(t); 1.85(m); 3.13(s);











3.27(s); 3.98(s); 7.94(d);











8.11(d)


4.37
Cl
SO2CH3
H
O
C2H5
C2H5
CH2
OH
0.91(t); 1.76(m); 3.12(s);











3.33(s); 8.07(dd); 13.75(s,











br).


4.38
Cl
SO2CH3
H
C(CH3)2
H
H
O
OH
1.34(s); 3.40(s); 4.13(s);











8.07(s); 13.95(s, br).


4.39
Cl
SO2CH3
H
O
CH3
H
CH2
Cl


4.40
Cl
SO2CH3
H
CH2
H
H
O
OH
>260


4.41
Cl
SO2CH3
H
CH2
H
H
O
OCH3
3.29(3H); 3.96(3H): 4.12(2H);











4.55(2H); 7.98(1H); 8.09(1H).


4.42
Cl
SCH3
H
O
H
H
CH2
OCH3
202-203


4.43
Cl
SO2CH3
H
O
COOMe
H
CHCO2CH3
OCH3
1.05(3H); 1.35(3H); 3.19(3H);











4.01(3H); 4.09(2H); 4.35(2H);











5.06(1H); 5.77(1H); 8.08(1H);











8.17(1H).


4.44
Cl
SO2CH3
H
O
CH3
H
O
OCH3
1.78(3H); 3.30(3H); 3.98(3H);











6.40(1H); 8.08(1H); 8.15(1H).


4.45
Cl
SO2CH3
H
O
CHO
H
CHCH3
OCH3
80-85


4.46
Cl
SO2CH3
H
O
CH3
H
CHCH2Cl
OCH3
1.65(3H); 3.27(3H); 3.50(2H);











4.00(3H); 4.22(1H); 4.88/5.08











(1H); 7.99(1H); 8.12(1H).


4.47
Cl
SO2CH3
H
O
CH3
H
CHCH2Cl
OH
100-105


4.48
Cl
SO2CH3
H
O
CHO
H
CHCH3
OH
180-185


4.49
Cl
SO2CH3
H
O
SC2H5
H
CH2
OCH3
1.30(3H); 2.75(2H); 3.25(1H);











3.34(3H); 3.78(1H); 3.94(3H);











6.22(1H); 8.15(2H).


4.50
Cl
SO2CH3
H
O
SC2H5
H
CH2
OH
65-67


4.51
Cl
SO2CH3
H
O
CH3
H
CHCH3
OCH3
1.01(3H); 1.28(3H); 3.33(4H);











3.96(3H); 4.98(1H); 8.12(1H);











8.20(1H).


4.52
Cl
SO2CH3
H
O
CH3
H
CHCH3
OH
68-75


4.53
Cl
SO2CH3
H
O
OCOCH3
H
CH2
OCH3
105-110


4.54
Cl
SO2CH3
H
O
H
H
CH2
OH


4.55
Cl
SO2CH3
H
O
OCOCH3
H
CH2
OH
45-50


4.56
Cl
SO2CH3
H
O
OCH3
H
CH2
OH
60-65


4.57
Cl
SO2CH3
H
O
CHCl(CH3)
H
CH2
OCH3
1.63(3H); 3.23(3H); 3.50(2H);











3.99(3H); 4.25(1H); 4.83/5.03











(1H); 7.96(1H); 8.13(1H).


4.58
Cl
SO2CH3
H
O
CHCl(CH3)
H
CH2
OH
1.56(3H); 3.33(3H); 3.43(2H);











4.36(1H); 4.93(1H); 8.10(2H).


4.59
Cl
SO2CH3
H
O
CH3
OCH3
CH2
OCH3
100-105


4.60
Cl
SO2CH3
H
O
CH3
OCH3
CH2
OH
40-45


4.61
Cl
SO2CH3
H
O
CF3
OCOCH3
CH2
OCH3
60-65


4.62
Cl
SCH3
H
O
H
H
CH2
OH


4.63
Cl
SO2Me
H
O
COCH3
H
CH2
OCH3
2.36(3H); 3.25(3H); 3.66(2H);











4.01(3H); 5.20(1H); 8.01(1H);











8.12(1H).


4.64
Cl
SO2CH3
H
O
CF3
H
CH2
OCH3
156


4.65
Cl
SO2CH3
H
O
CF3
H
CH2
OH
170


4.66
Cl
SO2CH3
H
O
F
F
CH2
OCH3


4.67
Cl
SO2CH3
H
O
F
F
CH2
OH


4.68
Cl
SO2CH3
H
O
F
H
CH2
OCH3
142-143


4.69
Cl
SO2CH3
H
O
F
H
CH2
OH


4.70
Cl
SO2CH3
H
O
CH2Cl
H
CH2
OCH3
107-110


4.71
Cl
SO2CH3
H
O
CH2Cl
H
CH2
OH
60-65


4.72
Cl
SO2CH3
H
O
OCH3
H
CH2
OCH3
105-110


4.73
Cl
SO2CH3
H
O
OC2H5
H
CH2
OCH3
155-160


4.74
Cl
SO2CH3
H
CH2
H
H
S
OCH3


4.75
CH3
H
H
C═O
H
H
S
OCH3
112-120


4.76
Cl
SO2CH3
H
O
CF3
OH
CH2
OH
3.38(s); 3.56(d); 3.79(d);











8.16(s); 8.67(s, br).


4.77
Cl
SO2CH3
H
O
O-t-C4H9
H
CH2
OCH3
130-135


4.78
Cl
SO2CH3
H
O
O-t-C4H9
H
CH2
OH
1.25(s); 3.05(dd); 3.34(s);











3.45(dd); 6.17(m); 8.08(s).


4.79
Cl
SO2CH3
H
O
CH3
H
CHCH3
OCH3
1.01(d); 1.28(d); 3.35(m);











3.96(s); 4.99(m); 8.12(d);











8.20(d).


4.80
Cl
SO2CH3
H
O
CH3
H
CHCH3
OH
68-75


4.81
Cl
SO2CH3
H
O
SC2H5
H
CH2
OCH3
1.30(t); 2.77(q); 3.25(dd);











3.34(s); 3.78(dd); 3.94(s);











6.22(m), 8.24(s).


4.82
Cl
SO2CH3
H
O
SC2H5
H
CH2
OH
65-67


4.83
SCH3
SCH3
H
O
H
H
CH2
OCH2CH3
1.28(t); 2.30(s); 2.46(s);











3.28(t); 4.31(q); 4.45(t);











7.42(d); 7.68(d).


4.84
SCH3
SCH3
H
O
H
H
CH2
OH
2.32(s); 2.48(s); 3.28(t);











4.42(t); 7.48(d); 7.64(d);











13.2(s).


4.85
SO2CH3
SO2CH3
H
O
H
H
CH2
OH
3.25(s); 3.35(s); 3.44(t);











8.05(d); 8.45(d).









The 3-heterocycly-substituted benzoyl derivatives of the formula I and their agriculturally useful salts are suitable as herbicides, both in the form of isomer mixtures and in the form of the pure isomers. The herbicidal compositions comprising compounds of the formula I effect very good control of vegetation on non-crop areas, especially at high rates of application. In crops such as wheat, rice, maize, soybeans and cotton they act against broad-leaved weeds and grass weeds without damaging the crop plants substantially. This effect is observed especially at low rates of application.


Depending on the application method in question, the compounds of the formula I, or herbicidal compositions comprising them, can additionally be employed in a further number of crop plants for eliminating undesirable plants. Examples of suitable crops are the following:



Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.


Moreover, the compounds of the formula I can also be used in crops which tolerate the action of herbicides due to breeding including genetic engineering methods.


The compounds of the formula I, or the herbicidal compositions comprising them, can be employed, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, also highly-concentrated aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend on the intended purposes; in any case, they should guarantee the finest possible distribution of the active ingredients according to the invention.


The herbicidal compositions comprise a herbicidally active amount of at least one compound of the formula I or of an agriculturally useful salt of I and auxiliaries conventionally used for the formulation of crop protection products.


Suitable inert auxiliaries are essentially:


mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strongly polar solvents, eg. amines such as N-methylpyrrolidone and water.


Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the substrates [sic], as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agent, tackifier, dispersant or emulsifier. However, it is also possible to prepare concentrates composed of active substance, wetting agent, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and these concentrates are suitable for dilution with water.


Suitable surfactants (adjuvants) are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, eg. ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, of alkyl- and alkylaryl sulfonates, of alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, and of fatty alcohol glycol ether, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphthalene, or of the naphthalenesulfonic acids, with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctyl-, octyl- or nonylphenol, alkylphenyl, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste liquors or methylcellulose.


Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.


Granules, eg. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic material, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders or other solid carriers.


The concentrations of the compounds of the formula I in the ready-to-use products can be varied within wide ranges. In general, the formulations comprise approximately from 0.001 to 98% by weight. preferably 0.01 to 95% by weight, of at least one active ingredient. The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).


The formulation examples below illustrate the preparation of such products:

    • I. 20 parts by weight of the compound No. 3.2 are dissolved in a mixture composed of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol of oleic acid N-monoethanolamide, 5 parts by weight of calcium dodecylbenzenesulfonate and 5 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.
    • II. 20 parts by weight of the compound No. 3.9 are dissolved in a mixture composed of 40 parts by weight of cyclohexanone, 30 parts-by weight of isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.
    • III. 20 parts by weight of the active ingredient No. 3.10 are dissolved in a mixture composed of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280° C. and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.
    • IV. 20 parts by weight of the active ingredient No. 3.16 are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalenesulfonate, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel and the mixture is ground in a hammer mill. Finely distributing the mixture in 20,000 parts by weight of water gives a spray mixture which compries 0.1% by weight of the active ingredient.
    • V. 3 parts by weight of the active ingredient No. 3.21 are mixed with 97 parts by weight of finely divided kaolin. This gives a dust which comprises 3% by weight of the active ingredient.
    • VI. 20 parts by weight of the active ingredient No. 3.22 are mixed intimately with 2 parts by weight of calcium dodecylbenzenesulfonate, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenol/urea/formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. This gives a stable oily dispersion.
    • VII. 1 part by weight of the active ingredient No. 3.34 is dissolved in a mixture composed of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. This gives a stable emulsion concentrate.
    • VIII. 1 part by weight of active ingredient No. 3.35 is dissolved in a mixture composed of 80 parts by weight of cyclohexanone and 20 parts by weight of WettolR EM 31 (=nonionic emulsifier based on ethoxylated castor oil). This gives a stable emulsion concentrate.


The compounds of the formula I, or the herbicidal compositions comprising them, can be applied pre- or post-emergence. If the active ingredients are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spray apparatus, in such a way that they come into as little contact as possible, if any, with the leaves of the sensitive crop plants while reaching the leaves of undesirable plants which grow underneath, or the bare soil (post-directed, lay-by).


Depending on the intended aim of the control measures, the season, the target plants and the growth stage, the application rates of the compound of the formula I are from 0.001 to 3.0, preferably 0.01 to 1.0 kg/ha of active substanz (a.s.).


To widen the spectrum of action and to achieve synergistic effects, the 3-heterocyclyl-substituted benzoyl derivatives of the formula I can be mixed and applied jointly with a large number of representatives of other groups of herbicidally or growth-regulatory active ingredients. Suitable components in mixtures are, for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and its derivatives, aminotriazoles, anilides, aryloxy-/hetaryloxyalkanic acids and their derivatives, benzoic acid and its derivatives, benzothiadiazinones, 2-(hetaroyl/aroyl)-1,3-cyclohexandiones, hetaryl aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinolinecarboxylic acid and its derivatives, chloroacetanilides, cyclohexenone oxime ether derivatives, diazines, dichloropropionic acid and its derivatives, dihydrobenzofuranes, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- and hetaryloxyphenoxypropionic esters, phenylacetic acid and its derivatives, 2-phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and its derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolcarboxamides and uracils.


Moreover, it may be advantageous to apply the compounds of the formula I, alone or in combination with other herbicides, in the form of a mixture with additional other crop protection agents, for example with pesticides or agents for controlling phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions which are employed for treating nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.


USE EXAMPLES

The herbicidal action of 3-heterocyclyl-substituted benzoyl derivatives of the formula I was demonstrated by the following greenhouse experiments:


The culture containers used were plastic flowerpots containing loamy sand with approximately 3.0% of humus as substrate. The seeds of the test plants were sown separately for each species.


For the pre-emergence treatment, the active ingredients, suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote germination and growth and subsequently covered with transparent plastic hoods until the plants had rooted. This cover causes [sic] uniform germination of the test plants unless this was adversely affected by the active ingredients.


For the post-emergence treatment, the test plants were grown to a plant height of from 3 to 15 cm, depending on the plant habit, and only then treated with the active ingredients which had been suspended or emulsified in water. To this end, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted into the test containers a few days prior to treatment. The rate of application for the post-emergence treatment was 31.2 or 15.6 g/ha a.s. (active substance).


Depending on the species, the plants were kept at from 10 to 25° C. and 20 to 35° C., respectively. The test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.


Evaluation was carried out using a scale of from 0 to 100. 100 means no emergence of the plants, or complete destruction of at least the aerial parts, and 0 means no damage or normal course of growth.


The plants used in the greenhouse experiments belonged to the following species:
















Scientific name
Common name










Chenopodium album

lambsquarters




(goosefoot)




Setaria faberii

giant foxtail




Sinapsis alba

white mustard




Solanum nigrum

black nightshade




Triticum aestivum

winter wheat




Zea mays

Indian corn










Compound 3.33 (Table 3) was very effective against the abovementioned mono- and dicotyledonous harmful plants and was well tolerated in winter wheat and maize when applied post-emergence at rates of application of 31.2 and 15.6 g/ha, respectively.

Claims
  • 1. A 3-heterocyclyl-substituted benzoic acid compound of formula III,
  • 2. The 3-heterocyclyl-substituted benzoic acid compound of formula III defined in claim 1, wherein R19 is halogen, hydroxyl or C1-C6-alkoxy.
  • 3. A 3-heterocyclyl-substituted benzoyl compound of formula I
  • 4. A composition comprising a herbicidally active amount of at least one 3-heterocyclyl-substituted benzoyl compound of formula I or of the agriculturally useful salt of formula I defined in claim 3, and auxiliaries conventionally used for the formulation of crop protection products.
  • 5. A process for the preparation of the composition defined in claim 4, which comprises mixing a herbicidally active amount of at least one 3-heterocyclyl-substituted benzoyl compound of the formula I or of the agriculturally useful salt of I and auxiliaries conventionally used for the formulation of crop protection products.
  • 6. A method of controlling undesirable vegetation, which comprises allowing a herbicidally active amount of at least one 3 -heterocyclyl-substituted benzoyl compound of the formula I or of the agriculturally useful salt of I defined in claim 3 to act on plants, their environment and/or on seeds.
  • 7. The 3-heterocyclyl-substituted benzoyl compound of the formula I defined in claim 3, wherein R1 is methyl, R2 is methylsulfonyl, R3 is hydrogen, R16 is methyl and R18 is hydrogen.
  • 8. The 3-heterocyclyl-substituted benzoyl compound of the formula I defined in claim 3, wherein R1 is methyl, R2 is methylsulfonyl, R3 is hydrogen, R16 is ethyl and R18 is hydrogen.
  • 9. The 3-heterocyclyl-substituted benzoyl compound of the formula I defined in claim 3, wherein R1 is methyl, R2 is methyl-sulfonyl, R3 is hydrogen, R16 is methyl and R18 is methyl.
  • 10. The 3-heterocyclyl-substituted benzoyl compound of the formula I defined in claim 3, wherein R1 is methyl.
  • 11. The 3-heterocyclyl-substituted benzoic acid compound of the formula III defined in claim 1, wherein R1 is methyl.
  • 12. The 3-heterocyclyl-substituted benzoic acid compound of the formula III defined in claim 2, wherein R1 is methyl.
  • 13. The 3-heterocyclyl-substituted benzoyl compound of the formula I defined in claim 3, wherein X is O;R1 is C1-C2-alkyl;R2 is C1-C6-alkylthio or C1-C6-alkylsulfonyl;R3 is hydrogen;Y is CR13R14; andR13, R14 are hydrogen or C1-C4-alkyl.
  • 14. The composition defined in claim 4, comprising a herbicidally active amount of at least one 3-heterocyclyl-substituted benzoyl compound of the formula I or of the agriculturally useful salt the formula of I, wherein X is O;R1 is C1-C2-alkyl;R2 is C1-C4-alkylthio or C1-C6-alkylsulfonyl;R3 is hydrogen;Y is CR13R 14; andR 13, R14 are hydrogen or C1-C4-alkyl.
  • 15. The 3-heterocyclyl-substituted benzoic acid compound of the formula III defined in claim 1, wherein X is O;R1 is C1-C2-alkyl;R2 is C1-C6-alkylthio or C1-C6-alkylsulfonyl;R3 is hydrogen;Y is CR13R14; andR13, R14 are hydrogen or C1-C4-alkyl.
Priority Claims (1)
Number Date Country Kind
197 01 446 Jan 1997 DE national
CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a 37 C.F.R. § 1.53(b) Divisional of U.S. application Ser. No. 09/748,006 filed Dec. 27, 2000, now U.S. Pat. No. 7,232,792 which in turn is a Divisional of U.S. application Ser. No. 09/091,300 filed Jun. 16, 1998 which in turn claims priority of International Application No. PCT/EP98/00069 filed on Jan. 8, 1998. The entire contents of these applications are hereby incorporated by reference.

US Referenced Citations (11)
Number Name Date Kind
4070536 Konotsune et al. Jan 1978 A
4687858 Konotsune et al. Aug 1987 A
4948887 Baba et al. Aug 1990 A
4986845 Oya et al. Jan 1991 A
5846907 von Deyn et al. Dec 1998 A
6147031 Adachi et al. Nov 2000 A
6479437 Bratz et al. Nov 2002 B1
6613719 Kudis et al. Sep 2003 B1
6713436 Neidlein et al. Mar 2004 B1
6831039 Neidlein et al. Dec 2004 B1
7232792 von Deyn et al. Jun 2007 B2
Foreign Referenced Citations (4)
Number Date Country
203 428 Dec 1986 EP
WO-9626206 Aug 1996 WO
WO-9741105 Nov 1997 WO
WO-9746530 Dec 1997 WO
Related Publications (1)
Number Date Country
20080039327 A1 Feb 2008 US
Divisions (2)
Number Date Country
Parent 09748006 Dec 2000 US
Child 11739928 US
Parent 09091300 US
Child 09748006 US